CN114765097A - 电介质材料、陶瓷电子器件、电介质材料的制造方法及陶瓷电子器件的制造方法 - Google Patents
电介质材料、陶瓷电子器件、电介质材料的制造方法及陶瓷电子器件的制造方法 Download PDFInfo
- Publication number
- CN114765097A CN114765097A CN202210036938.3A CN202210036938A CN114765097A CN 114765097 A CN114765097 A CN 114765097A CN 202210036938 A CN202210036938 A CN 202210036938A CN 114765097 A CN114765097 A CN 114765097A
- Authority
- CN
- China
- Prior art keywords
- dielectric material
- ratio
- perovskite
- site
- sites
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003989 dielectric material Substances 0.000 title claims abstract description 48
- 239000000919 ceramic Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 238000000034 method Methods 0.000 claims description 46
- 238000000137 annealing Methods 0.000 claims description 33
- 238000010304 firing Methods 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 5
- 229910052693 Europium Inorganic materials 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 33
- 239000010936 titanium Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 28
- 239000003985 ceramic capacitor Substances 0.000 description 24
- 229910052761 rare earth metal Inorganic materials 0.000 description 23
- 229910002113 barium titanate Inorganic materials 0.000 description 15
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 13
- 239000012071 phase Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910010293 ceramic material Inorganic materials 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002253 near-edge X-ray absorption fine structure spectrum Methods 0.000 description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 4
- 238000010405 reoxidation reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
- 229910052689 Holmium Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 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 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 tetragonal compound Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
-
- 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
-
- 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
- C04B35/622—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
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
- H01G13/006—Apparatus or processes for applying terminals
-
- 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
- H01G4/005—Electrodes
- H01G4/012—Form of non-self-supporting electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- 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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- 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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
-
- 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
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
-
- 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
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
-
- 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
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- 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
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6025—Tape casting, e.g. with a doctor blade
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6582—Hydrogen containing atmosphere
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
- C04B2235/6584—Oxygen containing atmosphere, e.g. with changing oxygen pressures at an oxygen percentage below that of air
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6588—Water vapor containing atmospheres
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
- C04B2235/662—Annealing after sintering
- C04B2235/663—Oxidative annealing
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
- C04B2235/662—Annealing after sintering
- C04B2235/664—Reductive annealing
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/79—Non-stoichiometric products, e.g. perovskites (ABO3) with an A/B-ratio other than 1
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
本发明涉及一种电介质材料,其包括作为主相的钙钛矿以及具有+2价和+3价的Eu,该钙钛矿的A位至少包括Ba,该钙钛矿的B位至少包括Ti,且Eu的+2价比率为21%以上。
Description
技术领域
本发明的某方面涉及电介质材料、陶瓷电子器件、电介质材料的制造方法及陶瓷电子器件的制造方法。
背景技术
诸如层叠陶瓷电容器的陶瓷电子器件被用于高频通信设备如移动电话中,以消除噪声。这些设备需要具有小尺寸(薄尺寸)和大容量的陶瓷电子器件。在安装在车辆上的设备中,需要具有高额定电压和高可靠性的陶瓷电子器件。为满足这些需求,需要即使在每一单电介质层的电场负荷增加时也可确保可靠性的高度可靠的电介质材料。因此,公开了一种将稀土元素添加到钙钛矿中的技术(例如,见国际公开2008/105240)。公开了Eu用作稀土元素的效果(例如,见日本专利申请公开2016-169130)。
发明内容
然而,由于电介质材料上的负荷增大,导致可靠性不足。需要进一步提高可靠性的手段。
根据实施方式的第一方面,提供一种电介质材料,包括:作为主相的钙钛矿,该钙钛矿的A位至少包括Ba,该钙钛矿的B位至少包括Ti;以及具有+2价和+3价的Eu,其中Eu的+2价的比率为21%以上。
根据实施方式的第二方面,提供一种陶瓷电子器件,包括:层叠结构,在该层叠结构中多个电介质层和多个内部电极层交替堆叠,其中多个电介质层的材料是电介质材料。
根据实施方式的第三方面,提供一种电介质材料的制造方法,包括:烧制电介质材料,在电介质材料中Eu被添加到A位至少包括Ba并且B位至少包括Ti的钙钛矿粉末中;以及在低于烧制工序温度的温度下并在低于烧制工序氧分压的氧分压下将烧制的电介质材料退火,其中退火工序的条件调节为使得Eu的+2价的比率为21%以上。
根据实施方式的第四方面,提供一种陶瓷电子器件的制造方法,包括:烧制层叠结构,在该层叠结构中电介质材料的片材和金属导电浆料的图案堆叠,Eu被添加到电介质材料的钙钛矿粉末,钙钛矿的A位至少包括Ba,钙钛矿的B位至少包括Ti;以及在低于烧制温度的温度下并在低于烧制氧分压的氧分压下将烧制的层叠结构退火,其中退火工序的条件调节为使得Eu的+2价的比率为21%以上。
附图说明
图1是层叠陶瓷电容器的部分截面透视图;
图2是沿图1中的A-A线得到的截面图;
图3是沿图1中的B-B线得到的截面图;
图4是制造层叠陶瓷电容器的方法的流程图;
图5示出对于实施例2的Eu的近L3吸收边XANES光谱;
图6示出对于实施例5的Eu的近L3吸收边XANES光谱;且
图7示出Eu的+2价的比率与寿命之间的关系。
具体实施方式
在下文中将参考附图对示例性实施方式进行说明。
[示例性实施例]
图1示出根据实施方式的层叠陶瓷电容器100的透视图,其中示出层叠陶瓷电容器100的部分截面。图2是沿图1中的A-A线得到的截面图。图3是沿图1中的B-B线得到的截面图。如图1至图3所示,层叠陶瓷电容器100包括具有长方体形状的层叠芯片10,以及分别设置在层叠芯片10的彼此相对的两个端面上的外部电极20a和20b。在层叠芯片10的两个端面以外的四个面中,将层叠芯片10在层叠方向的上下两面以外的两个面称为侧面。外部电极20a和20b各自延伸到层叠芯片10的层叠方向的上下两面以及两个侧面。然而,外部电极20a和20b彼此间隔开。
层叠芯片10具有被设计成具有交替堆叠的电介质层11和内部电极层12的结构。电介质层11包括用作电介质材料的陶瓷材料。内部电极层12的端缘交替地露出至层叠芯片10的第一端面和层叠芯片10的不同于第一端面的第二端面。外部电极20a设置在第一端面上。外部电极20b设置在第二端面上。因此,内部电极层12交替地电导接到外部电极20a和外部电极20b。因此,层叠陶瓷电容器100具有其中多个电介质层11层叠且内部电极层12介于其间的结构。在电介质层11和内部电极层12的层叠结构中,在层叠方向上的最外层是内部电极层12,覆盖层13覆盖层叠结构的上下两面。覆盖层13主要由陶瓷材料组成。例如,覆盖层13的主要成分与电介质层11的主要成分相同。
例如,层叠陶瓷电容器100可以具有0.25mm的长度、0.125mm的宽度和0.125mm的高度。层叠陶瓷电容器100可以具有0.4mm的长度、0.2mm的宽度和0.2mm的高度。层叠陶瓷电容器100可以具有0.6mm的长度、0.3mm的宽度和0.3mm的高度。层叠陶瓷电容器100可以具有1mm的长度、0.5mm的宽度和0.5mm的高度。层叠陶瓷电容器100可以具有3.2mm的长度、1.6mm的宽度和1.6mm的高度。层叠陶瓷电容器100可以具有4.5mm的长度、3.2mm的宽度和2.5mm的高度。然而,层叠陶瓷电容器100的尺寸并不限于上述尺寸。
内部电极层12主要由贱金属比如镍(Ni)、铜(Cu)或锡(Sn)组成。内部电极层12可以由贵金属比如铂(Pt)、钯(Pd)、银(Ag)或金(Au)或包括它们中的一种或多种的合金组成。
电介质层11主要由具有以通式ABO3表示的钙钛矿结构的陶瓷材料组成。钙钛矿结构包括具有非化学计量组成的ABO3-α。在该实施方式中,陶瓷材料的A位至少包括Ba(钡),并且陶瓷材料的B位至少包括Ti(钛)。B位可以包括Zr(锆)。
如图2所示,其中连接至外部电极20a的内部电极层12与连接至外部电极20b的内部电极层12相对的区域是层叠陶瓷电容器100中产生电容的区域。因此,该区域被称为电容区域14。即,电容区域14是其中连接到不同外部电极的两个相邻的内部电极层12彼此面对的区域。
其中连接到外部电极20a的内部电极层12彼此相对而不夹着连接到外部电极20b的内部电极层12的区域被称为端缘15。其中连接到外部电极20b的内部电极层12彼此相对而不夹着连接到外部电极20a的内部电极层12的区域也是端缘15。即,端缘15是其中连接到一个外部电极的内部电极层12彼此相对而不夹着连接到另一个外部电极的内部电极层12的区域。端缘15是其中不产生电容的区域。
如图3所示,在层叠芯片10中,从层叠芯片10的两个侧面各自到内部电极层12的区域被称为侧缘16。即,侧缘16是覆盖层叠的内部电极层12在朝着层叠结构的各侧面延伸的各个边缘的区域。侧缘16是不产生电容的区域。
认为可将稀土元素添加到电介质层11中以提高电介质层11的可靠性。然而,稀土元素比如Ho(钬)、Dy(镝)、Y(钇)等在B位比A位更易固溶。当大量的稀土元素固溶于B位时,受体量过剩。这造成氧空位,导致寿命降低。因此,寿命提高有限。
由此,本发明人研究了一种易固溶于BaTiO3的A位的具有大离子半径的稀土元素。本发明人已发现,相较于诸如Ho、Dy、Y等其它稀土元素,Eu(铕)将电介质层11的高温负荷寿命提高了约一个数量级。
稀土元素的化合价通常为+3。作为+3价的稀土元素,Eu也用于将钙钛矿改性。然而,Eu的特殊特性在于,除了+3,Eu还有另一稳定化合价,即+2。本发明人已经发现,当增加+2价的Eu时,高温负荷寿命显著提高。提高寿命效应的原因尚不清楚。然而,在可固溶于A位的稀土元素中,+2价Eu离子的离子半径最大。因此认为很有可能是Eu离子在很大程度上使钙钛矿晶格变形,降低氧空位运动所需的能量(活化能),而氧空位可能是寿命降低的主要因素。实际上,当将除Eu之外的不具有稳定+2价的稀土元素应用于实施方式时,寿命未得到提高。
表1示出稀土元素的离子半径,这些稀土元素的配位数为6。表1来源于“R.D.Shannon,Acta Crystallogr.,A32,751(1976年)”。
[表1]
本发明人已经发现,当在所有被添加到电介质层11的Eu中具有+2价的Eu的量为21%以上时,电介质层11的寿命得到提高,并且电介质层11的可靠性得到提高。认为大量的Eu可以固溶于A位。
从提高电介质层11可靠性的观点而言,优选在所有被添加到电介质层11的Eu中具有+2价的Eu的量(+2价的比率)为21%以上。更优选的是该比率为26%以上。
有利的是使大量+3价的Eu还原成+2价的Eu,以增加+2价的比率。然而,在用于还原Eu的退火工序中,在使+3价Eu还原成+2价Eu期间,可能在电介质层11中发生晶粒生长。当在电介质层11中发生晶粒生长时,电介质层11的寿命可能会降低。因此,当在电介质层11中发生晶粒生长时,由晶粒生长导致的寿命缩短的效应可能抵消由+2价Eu带来的寿命提高的效果。晶粒生长可能破坏内部电极层12的结构。这可能导致短路。因此,优选Eu的+2价比率具有上限。例如,优选在电介质层11中Eu的+2价比率为80%以下。更优选该比率为70%以下。还更优选该比率为59%以下。
当构成电介质层11主相的钙钛矿的A位具有空位时,在A位中形成足量的空间。而且,具有大离子半径和+2价的Eu易固溶于A位。因此,优选A位具有空位。例如,优选在构成电介质层11主相的钙钛矿中,A位/B位的原子浓度比率为0.980以下。更优选原子浓度比率为0.970以下。还更优选原子浓度比率为0.960以下。当A位元素仅为Ba并且B位元素仅为Ti时,A位/B位的原子浓度比率是Ba/Ti的原子浓度比率。当A位元素仅为Ba并且B位元素仅为Ti和Zr时,A位元素/B位元素的原子浓度比率是Ba/(Ti+Zr)的原子浓度比率。
当A位/B位的原子浓度比率过小时,由于正方晶特性低下,电介质层11的介电常数可能减小。优选A位/B位的原子浓度比率具有下限。优选在构成电介质层11主相的钙钛矿中,A位/B位的原子浓度比率为0.920以上。更优选原子浓度比率为0.940以上。还更优选原子浓度比率为0.950以上。
当B位包括Zr时,构成电介质层11主相的钙钛矿可以维持绝缘特性。从充分获得维持绝缘特性这一效果的观点而言,优选Zr/Ti比率(原子浓度比率)具有下限。优选Zr/Ti比率为0.01以上。更优选Zr/Ti比率为0.02以上。还更优选Zr/Ti比率为0.04以上。
在构成电介质层11主相的钙钛矿的B位包括Zr的情况下,当Zr的量过大时,在电介质层11的烧制期间可能发生晶粒生长。而且,不一定能实现长寿命。优选Zr/Ti比率具有上限。例如,优选Zr/Ti比率为0.14以下。更优选Zr/Ti比率为0.10以下。还更优选Zr/Ti比率为0.08以下。
当添加到电介质层11中的Eu量过小时,不一定能实现足够寿命。因此,优选添加到电介质层11中的Eu量具有下限。例如,优选在电介质层11中Eu相对于B位元素量的原子浓度比率(Eu/B位)为0.001以上。更优选原子浓度比率为0.005以上。还更优选原子浓度比率为0.010以上。当B位元素仅为Ti时,原子浓度比率(Eu/B位)意指Eu/Ti。当B位元素为Ti和Zr时,原子浓度比率(Eu/B位)意指原子浓度比率Eu/(Ti+Zr)。
当电介质层11中Eu的量过大时,绝缘特性可能低下,并且不一定能实现足够寿命。因此,优选添加到电介质层11中的Eu量具有上限。例如,优选Eu/B位的原子浓度比率为0.100以下。更优选原子浓度比率为0.060以下。还更优选原子浓度比率为0.040以下。
当电介质层11中Eu以外的稀土元素的量过大时,提高寿命的效果变弱。而且,不一定能实现充足的寿命。因此,优选Eu以外的稀土元素的量具有上限。具体来说,优选Eu以外的稀土元素的量小于Eu的量。当Eu以外的稀土元素的类型数量为两种以上时,优选稀土元素的总量小于Eu的量。
接下来,将描述层叠陶瓷电容器100的制造方法。图4是层叠陶瓷电容器100的制造方法的流程图。
[制造原材料粉末]
制备用于形成电介质层11的电介质材料。电介质层11中包含的A位元素和B位元素通常以ABO3颗粒烧结体的形式包含在电介质层11中。例如,BaTiO3是具有钙钛矿结构的四方化合物,并表现出高介电常数。BaTiO3通常可以通过将钛原材料比如二氧化钛与钡原材料比如碳酸钡反应以合成钛酸钡来获得。作为构成电介质层11的陶瓷的合成方法,已知有多种方法。例如,已知固相法、溶胶-凝胶法、水热法等等。在本实施方式中可以采用上述方法中的任一种。
根据目的可以将添加剂化合物添加到获得的陶瓷粉末中。添加剂化合物可以是Zr(锆)、Mg(镁)、Mn(锰)、V(钒)、Cr(铬)或Eu(铕)的氧化物,或Co(钴)、Ni(镍)、Li(锂)、B(硼)、Na(钠)、K(钾)或Si(硅)的氧化物,或玻璃。如有必要,可以是Eu以外的稀土元素的氧化物。该稀土元素是比如Sc(钪)、Y(钇)、La(镧)、Ce(铈)、Pr(镨)、Nd(钕)、Pm(钷)、Sm(钐)、Gd(钆)、Tb(铽)、Dy(镝)、Ho(钬)、Er(铒)、Tm(铥)、Yb(镱)或Lu(镥)。
例如,将包含添加剂的化合物与所得陶瓷材料粉末湿混。将所得陶瓷材料粉末干燥并粉碎。例如,如有必要,将所得陶瓷材料粉碎。因此,颗粒直径得到调节。或者,可以通过分级工序进一步调节粒径。由此,获得电介质材料。
[堆叠工序]
接下来,将粘合剂比如聚乙烯醇缩丁醛(PVB)树脂、有机溶剂比如乙醇或甲苯和增塑剂添加到所得电介质材料中并湿混。使用所得浆料,通过例如模涂机法或刮刀法将厚度为例如0.5μm以上的电介质生片涂布在基材上,然后干燥。
接下来,利用丝网印刷或凹版印刷,通过印刷用于形成内部电极的金属导电浆料,在电介质生片的表面上形成内部电极层图案。用于形成内部电极的金属导电浆料包含有机粘合剂。多个内部电极层图案交替露出至一对外部电极。向金属导电浆料中添加陶瓷颗粒作为共材。陶瓷颗粒的主要组分没有特别限制,但优选与电介质层11的主要组分陶瓷相同。例如,平均粒径为50nm以下的BaTiO3可以均匀分散。
之后,将其上印刷了内部电极层图案的电介质生片冲压成预定尺寸,并在剥离基材的同时堆叠预定数量(例如,100到1000)的冲压的电介质生片,使得内部电极层12和电介质层11彼此交替,并且内部电极层12的端缘交替露出到电介质层在长度方向上的两个端面,以便被交替引出到极性不同的一对外部电极。待成为覆盖层13的覆盖片被压着在堆叠方向上所堆叠的电介质生片的上下两面。并且,将所得层叠结构切割成预定的芯片尺寸(例如,1.0mm×0.5mm)。
[烧制工序]
在N2气氛中从所得的陶瓷层叠结构中除去粘合剂。之后,通过浸渍法涂覆待成为外部电极20a和20b的基层的Ni浆料。将所得陶瓷层叠结构在具有10-12到10-9atm的氧分压的还原气氛下在1160℃到1280℃的温度范围中烧制5分钟到10分钟。
[退火工序]
之后,在比烧制工序低的温度下并在比烧制工序更具还原性的气氛中执行退火工序。例如,退火工序在10-14MPa到10-13MPa的氧气压力下在1100摄氏度到1150摄氏度的还原气氛中持续1小时到2小时。优选退火工序的温度比烧制工序的最高温度低大约50摄氏度。
当在比烧制工序更具还原性的气氛中执行退火工序时,能够将+3价Eu还原为+2价。退火工序的条件可以调节为使得+2价的比率变为21%以上。
在烧制工序期间,能够像退火工序一样在强还原气氛中还原Eu。然而,在这种情况下,用作电介质层11主相的钛酸钡可能被还原。而且,可能产生大量的氧空位和大量的电子。氧空位是电介质层11寿命缩短的主要因素。因此,可靠性可能进一步降低。实际上,当使用将Eu充分还原成+2价的气氛时,钛酸钡本身强烈还原。在这种情况下,钛酸钡可能成为n型半导体。当钛酸钡在强还原气氛中长时间经受高温时,钛酸钡的颗粒会生长。在这种情况下,内部电极层12可能破坏。而且,容量可能降低。通过严格设计高温烧制条件和高精度控制炉内气氛,能够实现钛酸钡的抗还原性和Eu的还原。然而,工序并非用于批量生产层叠陶瓷电容器的一般工序。用于还原Eu的工序不受限制。但提出了一种在降温工序中包括上述强还原退火的工序,以便切实地实现提高使用寿命的效果。用于增加Eu的+2价比率的方法不限于上述方法。
[再氧化工序]
为了将氧气返回到在还原气氛中被烧制并被部分还原的用作电介质层11主相的钛酸钡中,可以在约1000摄氏度下的N2和水分的混合气体中或在500摄氏度到700摄氏度下的大气中执行热处理,使得内部电极层12不被氧化。该工序被称为再氧化工序。然而,执行一般再氧化工序,具有+2价的Eu可以被氧化成+3价。
因此,在实施方式中,再氧化工序在约900摄氏度下的N2气气氛中执行。当再氧化工序具有弱氧化条件时,能够在保持高比率的+2价Eu的同时使氧气返回到钛酸钡中。
[镀覆工序]
之后,可以通过镀覆在外部电极20a和20b的基层上形成金属层比如Cu、Ni、Sn等等。通过这些工序,制成层叠陶瓷电容器100。
能够通过使用XANES(X射线吸收近边结构)等来评估电介质层11的+2价Eu的比率。具体来说,使用同步辐射光源通过荧光法获得Eu的近L3吸收边光谱(6977eV)。背景被移除。根据+2价的峰面积(示出了影线)和+3价的峰面积(示出了影线)的比率计算+2价的比率(%)。峰面积的比率用下式表示。
(+2价峰面积)/{(+2价峰面积)+(+3价峰面积)}×100(%) (1)
Eu的+2价比率可以由层叠陶瓷电容器测量。或者,可通过压碎层叠陶瓷电容器获得粉末,并可将粉末变形成适合于样品评估的形状。其形态可以是电介质材料被成形为圆盘或方板并与层叠陶瓷电容器一起烧制而得到的块体(bulk body)。
[实施例]
制备了根据实施方式的层叠陶瓷电容器,并测量了层叠陶瓷电容器的特性。
(实施例1)制备钛酸钡粉末作为电介质材料。将添加剂(比如ZrO2、Eu氧化物、MnCO3、SiO2)添加到钛酸钡粉末中。将电介质材料和添加剂混合并通过使用为0.5mm的氧化锆球将其压碎。由此获得电介质材料。相对于100mol的主相(BaTiZrO3)添加1.0mol的Eu。相对于100mol的主相(BaTiZrO3)添加0.5mol的MnCO3。相对于100mol的主相(BaTiZrO3)添加1.0mol的SiO2。Ba/(Ti+Zr)为0.960。
将有机粘合剂和溶剂添加到所得的电介质材料中。使用所得浆料,通过刮刀法制备电介质生片。使用聚乙烯醇缩丁醛(PVB)等作为有机粘合剂。使用乙醇、甲苯等作为溶剂。向所得电介质材料添加增塑剂。
接下来,通过使用行星式球磨机制备用于形成内部电极层的金属导电浆料。金属导电浆料包括用作内部电极层12的主要组分金属的Ni、共材、粘合剂(乙基纤维素)、溶剂和必要时添加的添加剂。
通过丝网印刷在各个电介质生片上印刷用于形成内部电极层的金属导电浆料。将其中金属导电浆料被印刷在电介质生片上的片材部件层叠。在所堆叠的生片之上和之下堆叠覆盖片。之后,通过热压接获得层叠结构。层叠结构被切割成预定的形状。
在N2气氛中从所得层叠结构中去除粘合剂。之后,将包括主要组分为Ni的金属填料、共材、粘合剂、溶剂等等的金属导电浆料从层叠结构的两个端面到每个侧面进行涂覆并干燥。将用于基层的金属导电浆料和层叠结构在还原气氛中在1200℃温度下并在10-10MPa的氧分压下烧制10分钟。氧分压通过N2-H2-H2O的混合比率来调节。之后,将温度变为1140摄氏度。将氧分压变为10-13MPa。气氛保持2个小时。由此完成退火工序。之后,在约900摄氏度下在N2气气氛中执行再氧化工序。
层叠陶瓷的尺寸为1005尺寸(烧结结构的长度、宽度和高度为1.0mm、0.5mm和0.5mm)。电介质层的平均厚度为2.0μm。内部电极层的堆叠数量为100。
(实施例2)在实施例2中,退火工序的温度为1150摄氏度。其他条件与实施例1的条件相同。
(实施例3)在实施例3中,退火工序的温度为1160摄氏度。其他条件与实施例1的条件相同。
(实施例4)退火工序的氧分压为10-14MPa。其他条件与实施例1的条件相同。
(实施例5)在实施例5中,退火工序的温度为1150摄氏度,并且退火工序的氧分压为10-14MPa。其他条件与实施例1的条件相同。
(实施例6)在实施例6中,退火工序的温度为1160摄氏度,并且退火工序的氧分压为10-14MPa。其他条件与实施例1的条件相同。
(实施例7)在实施例7中,退火工序的温度为1150摄氏度,并且Ba/(Ti+Zr)为0.940。其他条件与实施例1的条件相同。
(实施例8)在实施例8中,退火工序的温度为1150摄氏度,并且Ba/(Ti+Zr)为0.920。其他条件与实施例1的条件相同。
(实施例9)在实施例9中,退火工序的温度为1150摄氏度,并且Ba/(Ti+Zr)为0.980。其他条件与实施例1的条件相同。
(比较例1)在比较例1中没有执行退火工序。其他条件与实施例1的条件相同。
(比较例2)在比较例2中,烧制工序的时间段为20分钟。其他条件与实施例9的条件相同。
(比较例3)在比较例3中,使用La代替Eu。其他条件与实施例2的条件相同。
(比较例4)在比较例4中,使用Gd代替Eu。其他条件与实施例2的条件相同。
(比较例5)在比较例5中,使用Dy代替Eu。其他条件与实施例2的条件相同。
(比较例6)在比较例6中,使用Ho代替Eu。其他条件与实施例2的条件相同。
(比较例7)在比较例7中,使用Er代替Eu。其他条件与实施例2的条件相同。
(化合价评估)对实施例1-9以及比较例1和2中的每一个评估电介质层中Eu的+2价比率。通过使用XANES评估Eu的+2价比率。图5示出实施例2中Eu的近L3吸收边XANES光谱(6977eV)。除+3价之外,+2价的峰值清楚地显现。根据图5的结果,实施例2中+2价的比率为26%。图6示出实施例5中Eu的近L3吸收边XANES光谱(6977eV)。根据图6的结果,实施例5中+2价的比率为43%。
实施例1的+2价比率为21%。实施例3的+2价比率为29%。实施例4的+2价比率为32%。实施例6的+2价比率为59%。实施例7的+2价比率为28%。实施例8的+2价比率为27%。实施例9的+2价比率为24%。表2示出结果。根据这些结果,当退火工序期间气氛的温度高或退火工序期间气氛的氧分压低时,+2价的比率就高。
[表2]
(评价寿命的方法)对实施例1-9和比较例1-7中的每一个,测量高温加速寿命测试(125摄氏度和50V/μm)的平均故障时间作为寿命。添加Eu制作的样品在通常烧制条件(比较例1)的寿命被设为是1.0。对实施例1-9和比较例2-7,测量相对于比较例1的寿命的寿命比。表1示出结果。当所测量的样品的寿命比为五倍以上时,因为寿命足够长,所以将样品判定为良好。当所测量的样品的寿命比小于五倍时,因为寿命不够长,所以将样品判定为不良。
图7示出Eu的+2价比率与寿命之间的关系。如图7所示,当+2价的比率为21%以上时,寿命变为比较例1的5倍以上。当+2价的比率为26%以上时,寿命变为比较例1的10倍以上。
相比之下,比较例3到7的寿命并不长。根据这些结果,Eu以外的稀土元素不能承受高负荷(比如125摄氏度和50V/m)。认为这是因为Eu以外的稀土元素的稳定化合价为+3,并且这些稀土元素的化合价不会变成+2。
当将实施例7和8与实施例2进行比较时,实施例7和8提高寿命的效果优于实施例2提高寿命的效果。认为这是因为实施例7和8的Ba/(Ti+Zr)小于实施例2的Ba/(Ti+Zr),A位的空位量增加,并且固溶Eu的量增加。
(介电常数的评价)对于实施例1-9和比较例1-7中的每一个,测量了介电常数和tanδ。表2示出结果。当将比较例1与实施例1进行比较时,介电常数和tanδ没有出现很大差异。因此,即使执行了退火工序,也不会发生显著的结构变化比如晶粒生长。当将比较例1与实施例2进行比较时,介电常数和tanδ没有出现很大差异。因此,即使执行实施例2的退火工序,也不会发生显著的结构变化比如晶粒生长。
在实施例6中,介电常数和tanδ增加。呈现晶粒生长的迹象。当还原工序的程度超过实施例6时,结构可能被改变。因此,可知优选Eu的+2价比率为59%以下。
当将实施例7与实施例8进行比较时,实施例8的介电常数开始降低。这意味着即使确保了长寿命,容量也可能减小。因此,优选Ba/(Ti+Zr)为0.940以上。
当将实施例1与比较例2进行比较时,+2价比率的差异小。然而,比较例2的相对寿命不是5.0倍以上。比较例2的介电常数和tanδ大于实施例1的介电常数和tanδ。认为这意味着钛酸钡的晶粒生长,并且由晶粒生长导致的寿命缩短效应抵消了+2价比率的效果。认为当Ba/(Ti+Zr)接近1.000的化学计量时,钛酸钡的反应性迅速增加。因此,优选Ba/(Ti+Zr)为0.960以下。
尽管已经详细描述了本发明的实施方式,但应理解,可以在不背离本发明的精神和范围的情况下对其进行各种更改、替换和改变。
Claims (19)
1.一种电介质材料,其包括:
作为主相的钙钛矿,所述钙钛矿的A位至少包括Ba,所述钙钛矿的B位至少包括Ti;以及
具有+2价和+3价的Eu,
其中Eu的+2价比率为21%以上。
2.根据权利要求1所述的电介质材料,其中Eu的+2价比率为26%以上。
3.根据权利要求1所述的电介质材料,其中Eu的+2价比率为29%以上。
4.根据权利要求1所述的电介质材料,其中Eu的+2价比率为32%以上。
5.根据权利要求1所述的电介质材料,其中Eu的+2价比率为43%以上。
6.根据权利要求1-5中任一项所述的电介质材料,其中Eu的+2价比率为80%以下。
7.根据权利要求1-5中任一项所述的电介质材料,其中Eu的+2价比率为70%以下。
8.根据权利要求1-5中任一项所述的电介质材料,其中Eu的+2价比率为59%以下。
9.根据权利要求1-8中任一项所述的电介质材料,其中所述钙钛矿中A位/B位的原子浓度比率为0.980以下。
10.根据权利要求1-8中任一项所述的电介质材料,其中所述钙钛矿中A位/B位的原子浓度比率为0.970以下。
11.根据权利要求1-8中任一项所述的电介质材料,其中所述钙钛矿中A位/B位的原子浓度比率为0.960以下。
12.根据权利要求1-11中任一项所述的电介质材料,其中所述钙钛矿中A位/B位的原子浓度比率为0.920以上。
13.根据权利要求1-11中任一项所述的电介质材料,其中所述钙钛矿中A位/B位的原子浓度比率为0.940以上。
14.根据权利要求1-11中任一项所述的电介质材料,其中所述钙钛矿中A位/B位的原子浓度比率为0.950以上。
15.根据权利要求1-14中任一项所述的电介质材料,其中Eu/所述B位的原子浓度比率为0.001以上。
16.根据权利要求1-14中任一项所述的电介质材料,其中Eu/所述B位的原子浓度比率为0.100以下。
17.一种陶瓷电子器件,其包括:
层叠结构,在所述层叠结构中多个电介质层和多个内部电极层交替堆叠,
其中所述多个电介质层的材料是如权利要求1-16中任一项所述的电介质材料。
18.一种电介质材料的制造方法,其包括以下工序:
烧制电介质材料,在所述电介质材料中Eu被添加到A位至少包括Ba且B位至少包括Ti的钙钛矿的粉末中;以及
在温度低于所述烧制工序的温度且氧分压低于所述烧制工序的氧分压的条件下将烧制的电介质材料退火,
其中所述退火工序的条件调节为使得Eu的+2价比率为21%以上。
19.一种陶瓷电子器件的制造方法,其包括以下工序:
烧制层叠结构,在所述层叠结构中电介质材料的片材和金属导电浆料的图案堆叠,Eu被添加到所述电介质材料的钙钛矿粉末中,所述钙钛矿的A位至少包括Ba,所述钙钛矿的B位至少包括Ti;以及
在温度低于烧制温度且氧分压低于烧制氧分压的条件下将烧制的层叠结构退火,
其中所述退火工序的条件调节为使得Eu的+2价比率为21%以上。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021-003742 | 2021-01-13 | ||
JP2021003742A JP2022108636A (ja) | 2021-01-13 | 2021-01-13 | 誘電体、セラミック電子部品、誘電体の製造方法、およびセラミック電子部品の製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114765097A true CN114765097A (zh) | 2022-07-19 |
Family
ID=78957632
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210036938.3A Pending CN114765097A (zh) | 2021-01-13 | 2022-01-13 | 电介质材料、陶瓷电子器件、电介质材料的制造方法及陶瓷电子器件的制造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US11837408B2 (zh) |
EP (1) | EP4029845A1 (zh) |
JP (1) | JP2022108636A (zh) |
KR (1) | KR20220102568A (zh) |
CN (1) | CN114765097A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210383973A1 (en) * | 2020-06-05 | 2021-12-09 | Taiyo Yuden Co., Ltd. | Multilayer ceramic capacitor and dielectric material |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2022108636A (ja) * | 2021-01-13 | 2022-07-26 | 太陽誘電株式会社 | 誘電体、セラミック電子部品、誘電体の製造方法、およびセラミック電子部品の製造方法 |
US20230093711A1 (en) * | 2021-09-17 | 2023-03-23 | Samsung Electro-Mechanics Co., Ltd. | Ceramic electronic component |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008105240A1 (ja) * | 2007-02-26 | 2008-09-04 | Murata Manufacturing Co., Ltd. | 誘電体セラミック、及び積層セラミックコンデンサ |
KR101646913B1 (ko) * | 2012-03-30 | 2016-08-09 | 다이요 유덴 가부시키가이샤 | 적층 세라믹 콘덴서 |
JP6387871B2 (ja) | 2015-03-13 | 2018-09-12 | Tdk株式会社 | 誘電体磁器組成物およびセラミック電子部品 |
JP6763175B2 (ja) * | 2016-03-30 | 2020-09-30 | Tdk株式会社 | 誘電体磁器組成物および積層セラミックコンデンサ |
US10957485B2 (en) * | 2018-03-06 | 2021-03-23 | Taiyo Yuden Co., Ltd. | Multilayer ceramic capacitor and ceramic material powder |
JP7441120B2 (ja) * | 2020-06-05 | 2024-02-29 | 太陽誘電株式会社 | 積層セラミックコンデンサおよび誘電体材料 |
JP2022108636A (ja) * | 2021-01-13 | 2022-07-26 | 太陽誘電株式会社 | 誘電体、セラミック電子部品、誘電体の製造方法、およびセラミック電子部品の製造方法 |
-
2021
- 2021-01-13 JP JP2021003742A patent/JP2022108636A/ja active Pending
- 2021-12-14 US US17/551,052 patent/US11837408B2/en active Active
- 2021-12-20 EP EP21215987.5A patent/EP4029845A1/en active Pending
-
2022
- 2022-01-05 KR KR1020220001491A patent/KR20220102568A/ko unknown
- 2022-01-13 CN CN202210036938.3A patent/CN114765097A/zh active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210383973A1 (en) * | 2020-06-05 | 2021-12-09 | Taiyo Yuden Co., Ltd. | Multilayer ceramic capacitor and dielectric material |
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 |
---|---|
US20220223346A1 (en) | 2022-07-14 |
JP2022108636A (ja) | 2022-07-26 |
EP4029845A1 (en) | 2022-07-20 |
KR20220102568A (ko) | 2022-07-20 |
US11837408B2 (en) | 2023-12-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102648161B1 (ko) | 적층 세라믹 콘덴서 및 그 제조 방법 | |
US10340084B2 (en) | Multilayer ceramic capacitor and manufacturing method of multilayer ceramic capacitor | |
US11017947B2 (en) | Multilayer ceramic capacitor and manufacturing method of multilayer ceramic capacitor | |
US20220230812A1 (en) | Multilayer ceramic capacitor having controlled concentration of rare earth element | |
JP7441120B2 (ja) | 積層セラミックコンデンサおよび誘電体材料 | |
KR102520018B1 (ko) | 적층 세라믹 콘덴서 및 그 제조 방법 | |
KR102442888B1 (ko) | 적층 세라믹 콘덴서 및 그 제조 방법 | |
CN114765097A (zh) | 电介质材料、陶瓷电子器件、电介质材料的制造方法及陶瓷电子器件的制造方法 | |
US11961674B2 (en) | Multilayer ceramic capacitor and ceramic material powder | |
US11769632B2 (en) | Ceramic capacitor having barium titanate-based dielectric layers including six sub-components | |
US20200402719A1 (en) | Ceramic electronic device and manufacturing method of the same | |
US11948747B2 (en) | Dielectric body, multilayer ceramic capacitor, manufacturing method of dielectric body, and manufacturing method of multilayer ceramic capacitor | |
US11834379B2 (en) | Ceramic raw material powder, multilayer ceramic capacitor and manufacturing method of multilayer ceramic capacitor | |
US20230274885A1 (en) | Dielectric material, multilayer ceramic electronic device, and manufacturing method of multilayer ceramic electronic device | |
JP2021158276A (ja) | セラミック原料粉末、セラミック電子部品の製造方法、およびセラミック原料粉末の製造方法 | |
KR20230120997A (ko) | 유전체 조성물, 적층 세라믹 전자 부품, 유전체 조성물의 제조 방법, 및 적층 세라믹 전자 부품의 제조 방법 | |
CN115101336A (zh) | 陶瓷电子器件和陶瓷电子器件的制造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |