WO2005090260A1 - 積層型セラミックコンデンサ - Google Patents
積層型セラミックコンデンサ Download PDFInfo
- Publication number
- WO2005090260A1 WO2005090260A1 PCT/JP2005/002885 JP2005002885W WO2005090260A1 WO 2005090260 A1 WO2005090260 A1 WO 2005090260A1 JP 2005002885 W JP2005002885 W JP 2005002885W WO 2005090260 A1 WO2005090260 A1 WO 2005090260A1
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- WIPO (PCT)
- Prior art keywords
- subcomponent
- oxide
- mol
- dielectric
- ceramic capacitor
- Prior art date
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- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 58
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 17
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 7
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 6
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 6
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 102
- 239000000203 mixture Substances 0.000 claims description 32
- 239000000919 ceramic Substances 0.000 claims description 17
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 14
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 13
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 claims description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- UFQXGXDIJMBKTC-UHFFFAOYSA-N oxostrontium Chemical compound [Sr]=O UFQXGXDIJMBKTC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims 1
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 35
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract 2
- 229910002976 CaZrO3 Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 92
- 238000010304 firing Methods 0.000 description 26
- 230000000694 effects Effects 0.000 description 23
- 238000000034 method Methods 0.000 description 17
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- 239000003990 capacitor Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 238000005245 sintering Methods 0.000 description 15
- 239000011575 calcium Substances 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 12
- 239000003989 dielectric material Substances 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 11
- 238000000137 annealing Methods 0.000 description 10
- 239000004020 conductor Substances 0.000 description 9
- 239000003981 vehicle Substances 0.000 description 9
- 229910052788 barium Inorganic materials 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 229910000990 Ni alloy Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000005684 electric field Effects 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 230000036961 partial effect Effects 0.000 description 7
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 5
- 239000010953 base metal Substances 0.000 description 5
- 239000002003 electrode paste Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052712 strontium Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- -1 CaCO Chemical class 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000008135 aqueous vehicle Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000003232 water-soluble binding agent Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- 241000234435 Lilium Species 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000005667 attractant Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000031902 chemoattractant activity Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/22—Nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
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Definitions
- the present invention relates to a multilayer ceramic capacitor, and more particularly, to a multilayer ceramic capacitor that has excellent capacitance with time and satisfies X8R characteristics.
- Multilayer ceramic capacitors as electronic components are widely used as small, large-capacity, high-reliability electronic components.
- demands for further miniaturization, higher capacity, lower cost, and higher reliability of multilayer ceramic capacitors have become more and more severe.
- a multilayer ceramic capacitor is generally formed by laminating a paste for an internal electrode layer and a paste for a dielectric layer by a sheet method, a printing method, or the like, and forming a laminate between the internal electrode layer and the dielectric layer in the laminate. It is manufactured by firing simultaneously.
- multilayer ceramic capacitors using a non-reducing dielectric material have a problem that IR (insulation resistance) is significantly degraded (that is, IR life is short) due to application of an electric field and reliability is low. There is.
- a capacitor may be used with a DC voltage superimposed on it.
- DC bias characteristics Characteristics (referred to as DC bias characteristics)
- Tc bias characteristic the capacitance-temperature characteristic at the time of applying a voltage is reduced.
- the dielectric layer is made thinner in order to reduce the size and increase the capacitance of the chip capacitor in response to recent demands, the electric field applied to the dielectric layer when a DC voltage is applied becomes stronger. The problem that the change with time, that is, the change with time of the capacitance becomes remarkably large, and the DC bias characteristics and the Tc bias characteristics are reduced are prominent.
- a capacitor is required to have good temperature characteristics, and in particular, it is required that the temperature characteristics be flat under severe conditions depending on the application.
- multilayer ceramic capacitors have been used for various electronic devices such as engine electronic control units (ECUs), crank angle sensors, and antilock brake system (ABS) modules installed in the engine room of automobiles. Is coming. Since these electronic devices are used to stably perform engine control, drive control, and brake control, good temperature stability of the circuit is required.
- ECUs engine electronic control units
- ABS antilock brake system
- the low (typically less than 100) makes it virtually impossible to make large capacitors.
- BaTiO is used as a dielectric ceramic composition having a high capacitance and a flat capacitance-temperature characteristic.
- the present applicant has already proposed the following dielectric porcelain composition for the purpose of satisfying the X8R characteristic having a high relative dielectric constant and enabling firing in a reducing atmosphere. (For example, see Patent Documents 1 and 2).
- Patent Document 1 discloses that a main component containing barium titanate, a first subcomponent containing at least one selected from MgO, CaO, Ba ⁇ , Sr ⁇ and CrO, and silicon oxide As an ingredient
- a third subcomponent containing R3 oxide (where R1 is at least one selected from Sc, Er, Tm, Yb and Lu); and a fourth subcomponent containing CaZrO or CaO + ZrO. 5
- the ratio of each component with respect to 100 moles of the main component is 0.1 to 3 moles for the first subcomponent, 2 to 10 moles for the second subcomponent, and 0.01 to 0.5 for the third subcomponent.
- Monole, 4th subcomponent 0.57 monole (however, the number of moles of 4th subcomponent is the ratio of R1 alone), 5th subcomponent: 0 ⁇ 5th subcomponent ⁇ 5 mol
- a porcelain composition is disclosed.
- Patent Document 2 discloses that a main component containing barium titanate, a first subcomponent containing an oxide of AE (here, AE is at least one selected from Mg, Ca, Ba and Sr), A second subcomponent containing an oxide of R (where R is at least one selected from Y, Dy, Ho and Er), and the ratio of each subcomponent to 100 moles of the main component is Disclosed is a dielectric porcelain composition in which 0 mol, 1 mol of the first sub-component and 0.1 mol, and 2 mol of the second sub-component are less than 7 mol.
- Patent Document 1 Patent No. 3348081
- Patent Document 2 Patent No. 3341003
- the thickness and thickness of the dielectric layer are further reduced.
- the present invention has been made to solve the above-described problems, and has an object to reduce the thickness and the multilayer of the dielectric layer for the purpose of miniaturization and large capacity, and to reduce the rated voltage. Even if improved, it is an object of the present invention to provide a multilayer ceramic capacitor whose capacitance-temperature characteristic satisfies the EIA standard X8R characteristic and whose capacitance changes with time.
- a multilayer ceramic capacitor according to the present invention includes a main component containing barium titanate, magnesium oxide (MgO), calcium oxide (CaO), and barium oxide (Ba ⁇ ). And at least one selected from strontium oxide (SrO), a second subcomponent containing silicon oxide as a main component, and vanadium oxide (VO).
- a third subcomponent consisting of an oxide of R1 (where R1 is at least one selected from Sc, Er, Tm, Yb and Lu); and a fourth subcomponent consisting of CaZrO or CaO + ZrO.
- the barium titanate having at least a subcomponent and a sixth subcomponent consisting of an R2 oxide (where R2 is at least one selected from Y, Dy, Ho, Tb, Gd and Eu);
- R2 is at least one selected from Y, Dy, Ho, Tb, Gd and Eu
- the ratio of each subcomponent to the moles is as follows: the first subcomponent: 0.1 to 3 mol, the second subcomponent: 210 mol, the third subcomponent: 0.01 to 0.5 monolayer, the fourth subcomponent.
- Component 0.5 to 7 moles (however, the number of moles of the fourth subcomponent is the ratio of R1 alone), the fifth subcomponent: more than 0 and 5 mol or less, and the sixth subcomponent: more than 0
- a laminated ceramic capacitor having a laminated body in which a dielectric layer made of a sintered body composed of crystal grains of a dielectric ceramic composition of not more than 9 moles and internal electrode layers are alternately laminated.
- the average grain size of the crystal grains constituting the dielectric layer is 0.5 to 0.55 zm.
- the multilayer ceramic capacitor of the present invention is the multilayer ceramic capacitor of the present invention, further comprising a seventh subcomponent made of manganese oxide (MnO) or chromium oxide (CrO). It is preferable that the ratio of the seventh subcomponent with respect to 100 moles of the barium titanate is 0.01 to 0.5 mole.
- the average grain size of crystal grains constituting the dielectric layer is 0.2111 to 0.35 ⁇ m. More preferred.
- the Tc bias characteristics are excellent.
- the multilayer ceramic capacitor of the present invention is the multilayer ceramic capacitor of the present invention described above, wherein the maximum grain size (D 100) and the average grain size (D5) of the crystal grains constituting the dielectric layer are different.
- D100-D50 value (hereinafter sometimes referred to as D100-D50 value) is less than or equal to 0.
- the Tc bias characteristics are excellent.
- the dielectric ceramic composed of such crystal grains is used.
- the bias characteristics are excellent. Therefore, when the dielectric layer is further thinned for the purpose of miniaturization and large capacity, or when the rated voltage is increased, its usefulness becomes remarkable. It is effective for use.
- the multilayer ceramic capacitor of the present invention can be fired in a reducing atmosphere since the dielectric ceramic composition used does not contain Pb, Bi, Zn, etc., and can be used under a DC electric field. There is also an effect that the change of the capacitance with time is small.
- FIG. 1 is a partially cutaway perspective view schematically showing one example of a multilayer ceramic capacitor of the present invention.
- FIG. 2 is a sectional view schematically showing a basic structure of a multilayer ceramic capacitor of the present invention. It is.
- FIG. 3 is a graph showing a relationship between an average particle diameter of dielectric particles (dielectric particles after sintering) constituting a dielectric layer and a capacitance-temperature characteristic (rate of change in capacitance).
- FIG. 4 is a graph showing a relationship between an average particle diameter of dielectric particles (dielectric particles after sintering) constituting a dielectric layer and a time-dependent change characteristic of capacitance (change rate of capacitance). is there.
- FIG. 5 is a graph showing a relationship between an average particle diameter of dielectric particles (dielectric particles after sintering) constituting a dielectric layer and Tc bias characteristics (rate of change in capacitance). .
- FIG. 6 is a graph showing a relationship between D100-D50 values of dielectric particles (dielectric particles after sintering) constituting a dielectric layer and Tc bias characteristics (rate of change in capacitance). .
- FIG. 7 is a graph showing a relationship between an average particle diameter of dielectric particles (dielectric particles after sintering) constituting a dielectric layer and an average life (average life time).
- FIG. 1 is a partially cutaway perspective view schematically showing an example of the multilayer ceramic capacitor of the present invention.
- FIG. 2 is a sectional view schematically showing a basic structure of the multilayer ceramic capacitor of the present invention.
- the multilayer ceramic capacitor of the present invention has a multilayer body in which dielectric layers 2 and internal electrode layers 3 are alternately stacked (hereinafter referred to as multilayer dielectric element body 10). Or the element body 10). At both ends of the laminated dielectric element body 10, the element body
- a pair of external electrodes 4 that are electrically connected to the internal electrode layers 3 alternately arranged inside 10 are formed. It is made.
- the shape of the multilayer dielectric element body 10 is usually a rectangular parallelepiped, but is not particularly limited. In addition, the dimensions are not particularly limited, but usually, the long side is about 0.6 to 5.6 mm, the short side is about 0.3 to 5. Omm, and the height is about 0.3 to 1.9 mm. .
- the dielectric layer 2 includes a main component containing barium titanate and at least one selected from magnesium oxide (Mg ⁇ ), calcium oxide (Ca ⁇ ), barium oxide (BaO), and strontium oxide (SrO). , A second sub-component containing silicon oxide as a main component, vanadium oxide (VO), molybdenum oxide (MoO) and tungsten oxide (WO
- R1 is at least one selected from Sc, Er, Tm, Yb and Lu.
- R1 is at least one selected from Sc, Er, Tm, Yb and Lu.
- a sintered body composed of crystal grains of a dielectric ceramic composition having at least a sixth subcomponent of at least one selected from Ho, Tb, Gd and Eu).
- the first subcomponent 0.1-3 mol
- the second subcomponent 2-10 mol
- the third subcomponent 0.01-0.5 mol
- the fourth subcomponent 0.5-7 mol
- 5th subcomponent 0 ⁇ 5th subcomponent ⁇ 5 mol
- 1st subcomponent 0.5-2.5 mol
- 2nd subcomponent 2.0-5.0 monolith
- Third subcomponent 0.1 to 0.4 monole
- 4th ij component 0.5 to 5.0 monole
- 5th ij component 0.5 to 3 monole
- 6th ij component 6th ij component:
- the above ratio of the fourth subcomponent is a molar ratio of R1 alone, not a molar ratio of R1 oxide. That is, for example, when an oxide of Yb is used as the fourth subcomponent, the fact that the ratio of the fourth subcomponent is 1 mol means that the ratio of YbO is not 1 mol, and that the ratio of YbO is 1 mol.
- barium titanate and each oxide constituting each subcomponent are represented by a stoichiometric composition, but the oxidation state of each oxide deviates from the stoichiometric composition. You may. However, the above ratio of each subcomponent is determined by converting the amount of metal contained in the oxide constituting each subcomponent to the above stoichiometric oxide.
- the first subcomponent is magnesium oxide (Mg ⁇ ), calcium oxide (CaO), barium oxide (B a ⁇ ) and strontium oxide (Sr ⁇ ) power At least one selected from the group consisting of: If the content of the first subcomponent is less than 0.1 mol, the rate of change in capacity with temperature will increase. On the other hand, when the content of the first subcomponent exceeds 1 mol, the sinterability deteriorates.
- the composition ratio of each oxide in the first subcomponent is arbitrary.
- the second subcomponent contains silicon oxide as a main component.
- the content of the second subcomponent is less than 2 mol, the capacity-temperature characteristics are deteriorated and the IR (insulation resistance) is reduced.
- the IR life becomes insufficient and the dielectric constant sharply decreases.
- These second subcomponents are mainly composed of silicon oxide (Si ⁇ ).
- MO where M is at least one element selected from Ba, Ca, Sr and Mg
- Li O lithium oxide
- B O boron oxide
- barium oxide (BaO) and calcium oxide (Ca) in [(Ba, Ca) SiO] are used.
- the complex oxide (Ba, Ca) SiO has a low melting point
- X in (Ba, Ca) SiO as a more preferred embodiment of the second subcomponent is preferably 0.7-7-1.2, more preferably
- the ratio between Ba and Ca is arbitrary, and may contain only one of them.
- the third sub-component is vanadium oxide (VO), molybdenum oxide (Mo ⁇ ), and tantalum oxide.
- This third subcomponent is
- the fourth subcomponent is composed of an oxide of R1 (however, R1 is at least one selected from Sc, Er, Tm, Yb and Lu forces).
- the fourth subcomponent has an effect of shifting the Curie temperature to a higher temperature side and an effect of flattening the capacitance-temperature characteristic.
- Yb oxide is preferred because of its high property improving effect and low price.
- the fifth subcomponent is composed of CaZrO or Ca ⁇ + Zr ⁇ . This fifth subcomponent is
- the addition form of the fifth subcomponent, CaZrO is not particularly limited.
- the ratio of Ca to Zr is not particularly limited, and may be determined so as not to form a solid solution with barium titanate.
- the molar ratio of Ca to Zr (Ca / Zr) is preferably 0.5-5. , More preferably 0.8-1.5, even more preferably 0.9-1.1.
- Adjustment can flatten the capacity-temperature characteristics (X8R characteristics) and improve the high-temperature accelerated life.
- the precipitation of the hetero-phase is suppressed, and the uniformity of the structure can be achieved.
- the sixth subcomponent is an oxide of R2 (where R2 is at least one selected from Y, Dy, Ho, Tb, Gd and Eu).
- the sixth subcomponent has an effect of improving IR and IR life, and has little adverse effect on capacitance-temperature characteristics.
- the content of R2 per 100 mol of titanium titanate is preferably 9 mol or less, more preferably 0.5-9 mol.
- Y oxide is preferred because it has a high property improving effect and is inexpensive.
- the total content of the fourth subcomponent and the sixth subcomponent is based on 100 mol of barium titanate. It is preferably 13 mol or less, more preferably 10 mol or less (however, the number of moles of the fourth subcomponent and the sixth subcomponent is a ratio of R1 and R2 alone), and the sinterability is preferably maintained. Can be.
- the dielectric ceramic composition may contain manganese oxide (Mn () or chromium oxide (Cr ⁇ ) as a seventh subcomponent.
- the seventh subcomponent has an effect of promoting sintering, an effect of increasing IR, and an effect of improving IR life.
- the ratio of the seventh subcomponent to 100 mol of barium titanate is preferably 0.01 mol or more.
- the content of the seventh subcomponent is too large, the capacity-temperature characteristics are adversely affected, so the content is preferably 0.5 mol or less.
- the number of moles of the seventh subcomponent is the ratio of Mn or Cr alone.
- Al O does not significantly affect the capacity-temperature characteristics
- the content of Al 2 O 3 is preferably set to 100 mol of barium titanate because the IR is lowered.
- the Curie temperature (phase transition temperature from ferroelectric to paraelectric) of the above-mentioned dielectric ceramic composition can be changed by selecting the composition of the dielectric ceramic composition.
- the temperature is preferably set to 120 ° C. or higher, more preferably 123 ° C. or higher.
- the lily temperature can be measured by DSC (differential scanning calorimetry) or the like.
- at least one kind of Sr, Zr, and Sn At least one kind of Sr, Zr, and Sn. Temperature characteristics deteriorate. Therefore, it is preferable not to use a barium titanate-based composite oxide containing these elements [eg, (Ba, Sr) TiO] as a main component.
- dielectric particles the crystal particles constituting the dielectric layer 2 (hereinafter referred to as “dielectric particles”) will be described.
- the average particle diameter of the dielectric particles is less than 0.2 ⁇ m, when the dielectric layer 2 is thinned (for example, when the thickness between layers is smaller than 3.5 zm), or when the dielectric layer 2 is laminated.
- the dielectric element body 10 is multi-layered (for example, when the number of the dielectric layers 2 is 100 or more), the X8R characteristics may not be satisfied. If the average particle diameter of the dielectric particles exceeds 0.55 am, the capacitance may change with time, and the capacitor may not be used as a stable capacitor.
- the dielectric particles preferably have an average particle diameter of 0.3 or more and 0.35 ⁇ m or less.
- the manufactured multilayer ceramic capacitor has the above-mentioned characteristics that the capacitance-temperature characteristics satisfy the X8R characteristics of the EIA standard and the capacitance changes with time are small. In addition to this, it has the effect of having excellent Tc bias characteristics.
- the average particle diameter of the dielectric particles is 0.35 ⁇ or less, a multilayer ceramic capacitor having excellent Tc bias characteristics can be obtained.
- the difference (D100 ⁇ D50 value) between the maximum particle size (D100) and the average particle size (D50) of the dielectric particles is preferably 0.4 / im or less. Since the dielectric particles have a D100_D50 value of 0.4 ⁇ or less, the manufactured multilayer ceramic capacitor has the capacitance-temperature characteristics that meet the X standard X8R characteristics and the capacitance changes over time are small. In addition to the above characteristics, it has the effect of being excellent in Tc bias characteristics.
- the average particle size of the dielectric particles is determined by a code method.
- the D100-D50 value represents the difference between the maximum particle size (D100) and the average particle size (D50) of the dielectric particles.
- the particle size distribution of the dielectric particles constituting the particle size is calculated in advance, and is calculated using the maximum particle size and the average particle size obtained from the particle size distribution.
- a small D100-D50 value means that the dispersion of the size of the dielectric particles constituting the dielectric layer 2 is small.
- JIS standard B characteristic Capacity change rate within ⁇ 25% at _25 85 ° C (standard temperature 20 ° C)
- the term "excellent change in capacitance with time” means that, for example, when a manufactured multilayer ceramic capacitor is applied at a temperature of 85 ° C and a DC voltage of 7 V / zm is applied, for example, after 1 000 hours. It means that the rate of change of capacity at is within 10%.
- the term "excellent in Tc bias characteristics" means that a manufactured multilayer ceramic capacitor usually has a capacitance of 0.02 VZ xm or more, particularly 0.2 V / zm or more, further 0.5 V / zm or more, and generally 5 V / zm or more. Even when an AC electric field of about am or less and a DC electric field of 5 VZ ⁇ m or less are superimposed on the AC electric field, the temperature characteristics of the capacitance are stable, and the capacitance change rate at Tc bias is 40%, for example. Means within.
- the thickness of the dielectric layer 2 is usually 30 / m or less. From the viewpoint of miniaturization and large capacity, the thickness of the dielectric layer 2 is preferably set to 10 ⁇ or less.
- the multilayer ceramic capacitor having the dielectric layer 2 thinned in this way can realize the miniaturization and large capacity, and the average particle diameter of the dielectric particles constituting the dielectric layer 2 is specified. This is effective for improving the capacity-temperature characteristics.
- the lower limit of the thickness of the dielectric layer 2 is not particularly limited, but it is about 0.5 ⁇ at best.
- the number of stacked dielectric layers 2 is usually about 50 to 1000.
- the internal electrode layers 3 are provided alternately with the dielectric layers 2 described above, and are laminated so that each end face is alternately exposed on the surface of two opposing ends of the laminated dielectric element body 10. There. Further, a pair of external electrodes 4 are formed at both ends of the multilayer dielectric element body 10 and connected to the exposed end faces of the nickel internal electrode layers 3 arranged alternately to constitute a multilayer ceramic capacitor. .
- the internal electrode layer 3 is composed of a base metal conductive material that substantially acts as an electrode.
- Ingredient Physically, Ni or a Ni alloy is preferable.
- the Ni alloy it is preferable that an alloy of Ni and one or more of Mn, Cr, Co, Al, W, etc. and Ni has a Ni content of 95% by weight or more.
- various trace components such as P, C, Nb, Fe, CI, B, Li, Na, K, F, and S may be contained in the Ni or Ni alloy in an amount of 0.1% by weight or less.
- Various conditions such as the number of layers and the thickness of the internal electrode layer 3 may be appropriately determined according to the purpose and application, but the thickness is generally preferably about 0.3 force S, and more preferably 0.2. .
- the external electrodes 4 are electrodes which are electrically connected to the internal electrode layers 3 alternately arranged inside the multilayer dielectric element main body 10, and are formed as a pair at both ends of the multilayer dielectric element main body 10.
- the outer B electrode 4 at least one kind of Ni, Pd, Ag, Au, Cu, Pt, Rh, Ru, Ir, or the like, or an alloy thereof can be used. Usually, Cu, Cu alloy, Ni or Ni alloy, Ag, Ag_Pd alloy, In-Ga alloy and the like are used.
- the thickness of the external electrode 4 may be appropriately determined according to the application and the like, but is usually preferably about 10 to 200 x m.
- a green chip is manufactured by a normal printing method or sheet method using a paste, and after firing, a green chip is printed or transferred to an external electrode. It is manufactured by firing.
- the manufacturing method will be specifically described.
- the dielectric layer paste may be an organic paint obtained by kneading a dielectric material and an organic vehicle, or may be an aqueous paint.
- the dielectric material As the dielectric material, the above-mentioned oxides, their mixtures, and composite oxides can be used.
- various compounds that become the above-mentioned oxides and composite oxides by firing such as carbonates, It can be appropriately selected from oxalates, nitrates, hydroxides, organometallic compounds, and the like, and used as a mixture.
- the content of each compound in the dielectric material may be determined so that the composition of the dielectric ceramic composition described above after firing is obtained.
- powder having an average particle size of about 0.1 to 3 zm is usually used. The desired average particle size can be obtained by appropriately adjusting the mixing time of the raw materials.
- the organic vehicle is obtained by dissolving a binder in an organic solvent.
- the binder is not particularly limited, and may be appropriately selected from ordinary various binders such as ethyl cellulose and polyvinyl butyral.
- the organic solvent to be used is not particularly limited, and may be appropriately selected from various organic solvents such as terbineol, butyl carbitol, acetone, and toluene, depending on the method to be used, such as a printing method or a sheet method.
- the dielectric layer paste is an aqueous paint
- an aqueous vehicle in which a water-soluble binder / dispersant or the like is dissolved in water may be kneaded with a dielectric material.
- the water-soluble binder used for the aqueous vehicle is not particularly limited, and for example, polyvinyl alcohol, cellulose, water-soluble acrylic resin, etc. may be used.
- the internal electrode layer paste is made of a conductive material made of the above-mentioned various dielectric metals or alloys, or various oxides, organometallic compounds, resinates, etc. which become the above-mentioned conductive material after firing, and the above-mentioned organic vehicle. And kneaded.
- the external electrode paste may be prepared in the same manner as the internal electrode layer paste described above.
- each of the above-mentioned pastes is not particularly limited, and may be a usual content, for example, about 115% by weight of a binder and about 10-50% by weight of a solvent.
- each paste may contain additives selected from various dispersants, plasticizers, dielectrics, insulators, and the like, if necessary.
- the total content of these is preferably not more than 10% by weight.
- the paste for the dielectric layer and the paste for the internal electrode layer are laminated and printed on a substrate such as PET, cut into a predetermined shape, and then separated from the substrate to form a green chip.
- a green sheet is formed using a dielectric layer paste, and an internal electrode layer paste is printed thereon, and then laminated to form a green chip.
- the green chip Before firing, the green chip is subjected to a binder removal treatment.
- the binder removal treatment may be performed under ordinary conditions.However, when a base metal such as Ni or a Ni alloy is used as the conductive material of the internal electrode layer, the heating rate is preferably set to 5300 ° CZ hours in an air atmosphere. , More preferably 10 to 100 ° C / hour, the holding temperature is preferably 180 to 400 ° C, more preferably 200 to 300 ° C, and the temperature holding time is preferably 0.5 to 24 hours, more preferably 5 to 24 hours. — 20 hours.
- the atmosphere during firing of the green chip depends on the type of conductive material in the internal electrode layer paste. Flip and may be suitably determined, but when using a base metal such as Ni or Ni alloy as the conducting material, the oxygen partial pressure in the firing atmosphere is 10_ 8 - is preferably a 10_ 12 atmospheres. When the oxygen partial pressure is less than the above range, the conductive material of the internal electrode layer may abnormally sinter and break. When the oxygen partial pressure exceeds the above range, the internal electrode layer tends to be oxidized.
- the holding temperature during firing is preferably 1100 to 1400. C, more preferably 1200-1360 ° C, even more preferably 1200-1340 ° C. If the holding temperature is lower than the above range, the densification becomes insufficient. If the holding temperature is higher than the above range, the electrode is interrupted due to abnormal sintering of the internal electrode layer, the capacity temperature characteristics deteriorate due to the diffusion of the internal electrode layer constituent material, and the dielectric Reduction of the body porcelain composition is likely to occur.
- the heating rate is preferably 50 to 500 ° CZ time, more preferably 200 to 300 ° CZ time, and the temperature holding time is preferably 0.58 hours, more preferably 11 to 10 hours.
- the cooling rate is preferably 50-500 ° C / hour, more preferably 200-300 ° C / hour.
- the atmosphere gas in which the firing atmosphere is preferably a reducing atmosphere, for example, a mixed gas of N and H is preferably used after being humidified.
- Annealing is a process for re-oxidizing the dielectric layer, which can significantly increase the IR lifetime, thereby improving reliability.
- An oxygen partial pressure in Aniru atmosphere, 10 1Q pressure or more, particularly 10 7 - is preferably a 10- 6 atm. If the oxygen partial pressure is less than the above range, it is difficult to reoxidize the dielectric layer, and if it exceeds the above range, the internal electrode layer tends to be oxidized.
- the holding temperature at the time of annealing is 1100 ° C or less, particularly 500 1100 ° C. If the holding temperature is lower than the above range, the oxidation of the dielectric layer becomes insufficient, so that the IR is low and the IR life is likely to be short. On the other hand, if the holding temperature exceeds the above range, not only the internal electrode layer is oxidized and the capacity is reduced, but also the internal electrode layer reacts with the dielectric substrate, deterioration of the capacity-temperature characteristic, and deterioration of IR. And IR life is likely to decrease. Note that the anneal may be composed of only a temperature raising process and a temperature lowering process. That is, the temperature holding time may be set to zero.
- the holding temperature is synonymous with the maximum temperature.
- Other annealing conditions include a temperature holding time of preferably 0 to 20 hours, more preferably 6 to 10 hours, and a cooling rate of preferably 50 to 500 ° C / hour, more preferably 100 to 100 hours. 300 ° C / hour.
- the ambient gas for anneal for example, humidified N
- N gas, mixed gas, and the like are calorie-treated.
- a wetter or the like may be used for wetting.
- the water temperature is preferably about 575 ° C.
- the binder removal treatment, firing and annealing may be performed continuously or independently.
- the atmosphere is changed without cooling, the temperature is raised to the holding temperature at the time of firing, firing is performed, and then cooling is performed, and the temperature reaches the holding temperature of anneal. It is preferable to sometimes change the atmosphere and perform annealing.
- the firing must be performed until the holding temperature at the time of binder removal is reached.
- the atmosphere After raising the temperature to the holding temperature under N gas atmosphere, the atmosphere may be changed
- the whole process of anneal can be converted into a humidified N gas atmosphere.
- the multilayer dielectric element body obtained as described above is subjected to edge polishing by, for example, barrel polishing or sandblasting, and the external electrode paste is printed or transferred and baked to form the external electrode 4. .
- the firing conditions for the external electrode paste are, for example,
- the temperature is preferable to set the temperature to about 600 to 800 ° C for 10 minutes to about 11 hours in a 22 mixed gas. Then, if necessary, a coating layer is formed on the surface of the external electrode 4 by plating or the like.
- the multilayer ceramic capacitor of the present invention thus manufactured is mounted on a printed circuit board or the like by soldering or the like, and is used for various electronic devices and the like.
- the present invention is not limited to such embodiments and does not depart from the gist of the present invention and falls within the scope. Of course, it can be implemented in various modes.
- a main component material BaTiO 3
- first to seventh subcomponent materials each having an average particle size of 0.1 1 lzm were prepared.
- the average particle size of the raw material powder is about 0.1-0.33 ⁇
- the specific surface area measured by the two-contact method is in the range of 3 to 8.5, specifically, the specific surface area force synthesized by the solid-phase method 7, 3.5, 3. 8, 4.1. , 4.4, 4.8, 5.0, 5.4, 6.0, 7.0, 7.
- i ⁇ can be obtained not only by the solid phase method but also by a general liquid phase synthesis.
- the raw material of MgO and MnO is carbonate (first subcomponent: MgCO, seventh subcomponent: MnC ⁇ ).
- the other raw materials are oxides (second subcomponent: (Ba Ca) SiO, third subcomponent: V O,
- (Ba Ca) SiO which is a sub-component, is obtained by adding BaCO, CaCO and Si
- the fifth subcomponent, CaZrO is
- VO as the 3rd ij component is 0.006 monole
- YbO as the 4th IJ component is 2.00 monole
- a green sheet having a thickness of 4 was formed on the PET film using the above-mentioned dielectric layer paste, and the internal electrode layer paste was printed thereon. did.
- these green sheets and a protective green sheet were laminated and pressed to obtain a green chip.
- the number of stacked sheets having internal electrodes was four.
- the green chip was cut into a predetermined size, subjected to binder removal treatment, fired, and annealed to obtain a fired multilayer ceramic body.
- the binder removal treatment was performed under the conditions of a heating time of 15 ° C / hour, a holding temperature of 280 ° C, a holding time of 8 hours, and an air atmosphere.
- the firing was performed at a heating rate of 200 ° C / hour, a holding temperature of 1270 to 1320 ° C, a holding time of 2 hours, a cooling rate of 300 ° C / hour, a humidified N + H mixed gas atmosphere (oxygen partial pressure was 10 11 bar)
- the annealing was performed under the conditions of a holding temperature of 900 ° C, a temperature holding time of 9 hours, a cooling rate of 300 ° C / hour, and a humidified N gas atmosphere (oxygen partial pressure is 10 to 7 atm). In addition, at the time of firing
- a wetter with a water temperature of 20 ° C was used to humidify the atmosphere gas, and a wetter with a water temperature of 30 ° C was used to humidify the atmosphere gas during annealing.
- the external electrode paste was transferred to the end face, and the paste was baked at 800 ° C. for 10 minutes in a humidified N + H atmosphere.
- An external electrode was formed by sintering to obtain a sample of the multilayer ceramic capacitor.
- Microscope Take a photograph, process the image, calculate the equivalent circle diameter of 300 crystal grains, and calculate the maximum particle diameter (D100) and average particle diameter obtained from the cumulative frequency distribution of these equivalent circle diameters. (D50).
- D100 maximum particle diameter
- D50 average particle diameter obtained from the cumulative frequency distribution of these equivalent circle diameters.
- the average particle size and the D100-D50 value of the dielectric particles were obtained from the particle size data of 300 crystal particles.
- the number of particle size data required was always 300. Other numbers may be used if necessary.
- each sample obtained was 3.2 mm X l. 6 mm X O. 6 mm, the number of dielectric layers sandwiched between the internal electrode layers was 4, and the thickness of each dielectric layer was 4 The thickness was 3. The thickness of each internal electrode layer was 1. O xm.
- the obtained multilayer ceramic capacitor sample was not reduced even when fired in a reducing atmosphere, and nickel used as an internal electrode was not oxidized to the extent that IR failure occurred.
- the capacitance temperature characteristics, the capacitance change characteristics over time, the Tc bias characteristics, and the average life were evaluated.
- the change with time of the capacitance is as follows: The static capacitance of the obtained capacitor sample before and after 1000 hours when a DC voltage of 7. OVZ xm was applied under a temperature environment of 85 ° C. Evaluation was made by measuring the rate of change (%) of the capacitance. Use LCR meter for capacitance measurement The samples around 1000 hours were measured under the conditions of frequency 1kHz and input signal level lVrms, and the results are shown in Table 1 and Fig. 4. The measurement results were evaluated based on whether the rate of change in capacitance around 1000 hours was within 10%.
- the Tc bias characteristic is the change in capacitance when a DC voltage of 7.0 V / zm is applied to the obtained capacitor sample at a temperature of 55 + 150 ° C. It was evaluated by measuring the rate (%). The capacitance was measured using an LCR meter at a frequency of 1 kHz and an input signal level of lVrms. The measurement results were evaluated based on whether the rate of change in capacitance was within 40%.
- Fig. 6 shows the results of a study on the relationship between the Tc bias characteristics and the D100-D50 values. As is clear from the results in FIG. 6, it was confirmed that when the D100-D50 value was 0.4 / m or less, the capacity change rate was within 40%.
- the average particle size of the dielectric particles constituting the dielectric layer As a result of evaluating the characteristics of samples having different diameters, the X8R characteristics were satisfied while the average particle size of the dielectric particles (dielectric particles after sintering) was in the range of 0.20 / 111 to 0.55 / im. The change with time of the capacity was within 10%. In addition, the dielectric particles (dielectric particles after sintering) satisfy the X8R characteristic when the average particle size is in the range of 0.20 to 0.35 zm, and the capacitance changes with time within 10%. The rate of capacitance change at the time of bias was within 40%. In addition, the D100-D50 value of the dielectric particles (dielectric particles after sintering) constituting the dielectric layer was 0.4 am or less, and the capacitance change rate at Tc bias was within 40%.
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JP2006282483A (ja) * | 2005-04-04 | 2006-10-19 | Tdk Corp | 電子部品、誘電体磁器組成物およびその製造方法 |
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US11776752B2 (en) * | 2020-06-05 | 2023-10-03 | Taiyo Yuden Co., Ltd. | Multilayer ceramic capacitor and dielectric material |
Also Published As
Publication number | Publication date |
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US7898793B2 (en) | 2011-03-01 |
EP1736456A4 (en) | 2010-09-22 |
KR100807774B1 (ko) | 2008-02-28 |
US20080253060A1 (en) | 2008-10-16 |
EP1736456A1 (en) | 2006-12-27 |
TWI263629B (en) | 2006-10-11 |
CN1930102A (zh) | 2007-03-14 |
EP1736456B1 (en) | 2013-10-23 |
JPWO2005090260A1 (ja) | 2008-01-31 |
KR20070026399A (ko) | 2007-03-08 |
TW200536806A (en) | 2005-11-16 |
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