TW201945320A - Multilayer ceramic capacitor and ceramic material powder - Google Patents
Multilayer ceramic capacitor and ceramic material powder Download PDFInfo
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- TW201945320A TW201945320A TW108107409A TW108107409A TW201945320A TW 201945320 A TW201945320 A TW 201945320A TW 108107409 A TW108107409 A TW 108107409A TW 108107409 A TW108107409 A TW 108107409A TW 201945320 A TW201945320 A TW 201945320A
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- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 37
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 27
- 239000000843 powder Substances 0.000 title claims description 53
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 76
- 239000006104 solid solution Substances 0.000 claims description 175
- 239000000919 ceramic Substances 0.000 claims description 56
- 239000002994 raw material Substances 0.000 claims description 48
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 14
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 14
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- 229910052779 Neodymium Inorganic materials 0.000 claims description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims description 12
- 229910052691 Erbium Inorganic materials 0.000 claims description 11
- 229910052693 Europium Inorganic materials 0.000 claims description 11
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 11
- 229910052772 Samarium Inorganic materials 0.000 claims description 11
- 229910052775 Thulium Inorganic materials 0.000 claims description 11
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 7
- 229910052689 Holmium Inorganic materials 0.000 claims description 7
- 229910052771 Terbium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims 1
- 238000009413 insulation Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 19
- 230000007547 defect Effects 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000010304 firing Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 206010021143 Hypoxia Diseases 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000010405 reoxidation reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010931 gold Substances 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
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- 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
- 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
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 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
- 238000010586 diagram Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000002349 favourable effect 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
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 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
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 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
- 238000005036 potential barrier Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 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
- 239000007787 solid Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- 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
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- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- 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
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- 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
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- 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
- H01G4/1236—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates
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- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1236—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates
- H01G4/1245—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates containing also titanates
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- H01G4/00—Fixed capacitors; Processes of their manufacture
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- H01G4/228—Terminals
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- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
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- 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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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- 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
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
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- 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
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
Description
本發明係關於一種積層陶瓷電容器及陶瓷原料粉末。The invention relates to a multilayer ceramic capacitor and ceramic raw material powder.
於介電層之厚度較小之積層陶瓷電容器中，要求可獲得充分之可靠性特性之介電材料。例如，判明預先使特定元素固溶於原料粉末之方法有效。專利文獻1揭示有以提昇壽命特性為目的而添加供體元素之技術。
[先前技術文獻]
[專利文獻]In multilayer ceramic capacitors having a small dielectric layer thickness, a dielectric material is required to obtain sufficient reliability characteristics. For example, it has been found that a method of dissolving a specific element in a solid powder in advance is effective. Patent Document 1 discloses a technique for adding a donor element for the purpose of improving life characteristics.
[Prior technical literature]
[Patent Literature]
[專利文獻1]日本專利特開2016-139720號公報[Patent Document 1] Japanese Patent Laid-Open No. 2016-139720
[發明所欲解決之問題][Problems to be solved by the invention]
然而，於介電層之厚度較小且積層數亦增加之近年來，要求進一步提昇壽命特性。又，亦要求提昇絕緣特性。因此，僅以藉由供體元素減少氧缺陷量之方法難以實現進一步之高可靠性。However, in recent years, the thickness of the dielectric layer is small and the number of stacked layers has also increased. In recent years, it is required to further improve the life characteristics. It is also required to improve the insulation characteristics. Therefore, it is difficult to achieve further high reliability only by reducing the amount of oxygen defects by the donor element.
本發明係鑒於上述問題而完成者，其目的在於提供一種可實現高可靠性之積層陶瓷電容器及陶瓷原料粉末。
[解決問題之技術手段]The present invention has been made in view of the above problems, and an object thereof is to provide a multilayer ceramic capacitor and a ceramic raw material powder that can achieve high reliability.
[Technical means to solve the problem]
本發明之積層陶瓷電容器之特徵在於：具備交替地積層有介電層與內部電極層之積層體；且上述介電層之主成分係陶瓷材料，該陶瓷材料以通式ABO3 所表示之鈣鈦礦結構為主相，於B部位包含作為供體而發揮功能之元素，A部位及B部位均包含稀土類元素；固溶於上述A部位之稀土類元素之固溶量(A部位固溶量)與固溶於上述B部位之稀土類元素之固溶量(B部位固溶量)之比滿足0.75≦(A部位固溶量/B部位固溶量)≦1.25。The multilayer ceramic capacitor of the present invention is characterized by having a multilayer body in which a dielectric layer and an internal electrode layer are alternately laminated; and the main component of the dielectric layer is a ceramic material, the ceramic material is calcium represented by the general formula ABO 3 The structure of titanium ore is the main phase. It contains elements that function as donors at the B site. Both the A and B sites contain rare earth elements. The solid solution content of the rare earth elements dissolved in the above A site (A site solid solution The ratio of the amount) to the solid solution amount of the rare earth elements (solid solution amount at the B site) in the B site satisfies 0.75 ≦ (solid solution amount at the A site / solid solution amount at the B site) ≦ 1.25.
於上述積層陶瓷電容器中，上述陶瓷材料可包含Ba及Ti。In the multilayer ceramic capacitor, the ceramic material may include Ba and Ti.
於上述積層陶瓷電容器中，上述作為供體而發揮功能之元素可包含Mo。In the multilayer ceramic capacitor, the element that functions as a donor may include Mo.
於上述積層陶瓷電容器中，上述稀土類元素可包含Tb、Dy、Ho及Y之至少任一者。In the multilayer ceramic capacitor, the rare earth element may include at least any one of Tb, Dy, Ho, and Y.
於上述積層陶瓷電容器中，上述A部位所包含之上述稀土類元素可包含La、Ce、Pr、Nd、Pm、Sm、Eu及Gd之至少任一者，上述B部位所包含之上述稀土類元素可包含Er、Tm及Yb之至少任一者。In the multilayer ceramic capacitor, the rare earth element contained in the A site may include at least any one of La, Ce, Pr, Nd, Pm, Sm, Eu, and Gd, and the rare earth element contained in the B site It may contain at least any one of Er, Tm, and Yb.
於上述積層陶瓷電容器中，積層方向上之上述介電層之厚度可為0.4 μm以下。In the multilayer ceramic capacitor, the thickness of the dielectric layer in the multilayer direction may be 0.4 μm or less.
於上述積層陶瓷電容器中，固溶於上述A部位之稀土類元素之固溶量(A部位固溶量)與固溶於上述B部位之稀土類元素之固溶量(B部位固溶量)之比可滿足0.95≦(A部位固溶量/B部位固溶量)≦1.05。In the multilayer ceramic capacitor described above, the solid solution amount of the rare-earth element solid-dissolved in the A part (the solid solution amount of the A part) and the solid solution amount of the rare earth element (the B-solid solution amount) in the B part The ratio can satisfy 0.95 ≦ (amount of solid solution in part A / amount of solid solution in part B) ≦ 1.05.
本發明之陶瓷原料粉末之特徵在於：以通式ABO3 所表示之鈣鈦礦結構為主相，於B部位包含作為供體而發揮功能之元素，A部位及B部位均包含稀土類元素；固溶於上述A部位之稀土類元素之固溶量(A部位固溶量)與固溶於上述B部位之稀土類元素之固溶量(B部位固溶量)之比滿足0.75≦(A部位固溶量/B部位固溶量)≦1.25。The ceramic raw material powder of the present invention is characterized in that: the perovskite structure represented by the general formula ABO 3 is the main phase; the B site contains elements that function as donors; the A site and the B site both contain rare earth elements; The ratio of the solid solution amount of the rare-earth elements solid-dissolved in the above-mentioned A part (the solid solution amount of the A part) to the solid-solution amount of the rare-earth elements in the above-mentioned B part (the solid solution amount of the B part) satisfies 0.75 ≦ (A Part solid solution amount / B part solid solution amount) ≦ 1.25.
上述陶瓷原料粉末可包含Ba及Ti。The ceramic raw material powder may include Ba and Ti.
於上述陶瓷原料粉末中，上述作為供體而發揮功能之元素可包含Mo。In the ceramic raw material powder, the element that functions as a donor may include Mo.
於上述陶瓷原料粉末中，上述稀土類元素可包含Tb、Dy、Ho及Y之至少任一者。In the ceramic raw material powder, the rare earth element may include at least any one of Tb, Dy, Ho, and Y.
於上述陶瓷原料粉末中，上述A部位所包含之上述稀土類元素可包含La、Ce、Pr、Nd、Pm、Sm、Eu及Gd之至少任一者，上述B部位所包含之上述稀土類元素可包含Er、Tm及Yb之至少任一者。In the ceramic raw material powder, the rare earth element contained in the A site may include at least any one of La, Ce, Pr, Nd, Pm, Sm, Eu, and Gd, and the rare earth element contained in the B site It may contain at least any one of Er, Tm, and Yb.
於上述陶瓷原料粉末中，固溶於上述A部位之稀土類元素之固溶量(A部位固溶量)與固溶於上述B部位之稀土類元素之固溶量(B部位固溶量)之比可滿足0.95≦(A部位固溶量/B部位固溶量)≦1.05。
[發明之效果]In the above-mentioned ceramic raw material powder, the solid solution amount of the rare-earth element solid-dissolved in the A part (the solid solution amount of the A part) and the solid solution amount of the rare earth element (the B-solid solution amount) dissolved in the B part The ratio can satisfy 0.95 ≦ (amount of solid solution in part A / amount of solid solution in part B) ≦ 1.05.
[Effect of the invention]
根據本發明，可提供一種可實現高可靠性之積層陶瓷電容器及陶瓷原料粉末。According to the present invention, it is possible to provide a multilayer ceramic capacitor and ceramic raw material powder that can achieve high reliability.
以下，一面參考圖式一面對實施形態進行說明。Hereinafter, embodiments will be described with reference to the drawings.
(實施形態)
圖1係實施形態之積層陶瓷電容器100之局部剖面立體圖。如圖1所例示，積層陶瓷電容器100具備：積層晶片10，其具有大致長方體形狀；外部電極20a、20b，其等設置於積層晶片10之任一對向之2個端面。再者，將積層晶片10之該2個端面以外之4個面中除積層方向之上表面與下表面以外之2個面稱為側面。外部電極20a、20b沿積層晶片10之積層方向之上表面、下表面及2個側面延伸。但，外部電極20a、20b相互隔開。(Implementation form)
FIG. 1 is a partial sectional perspective view of a multilayer ceramic capacitor 100 according to an embodiment. As shown in FIG. 1, the multilayer ceramic capacitor 100 includes a multilayer wafer 10 having a substantially rectangular parallelepiped shape, and external electrodes 20 a and 20 b provided on two opposite end surfaces of the multilayer wafer 10. It should be noted that, of the four surfaces other than the two end surfaces of the laminated wafer 10, two surfaces other than the upper surface and the lower surface in the lamination direction are referred to as side surfaces. The external electrodes 20 a and 20 b extend along the upper surface, the lower surface, and the two side surfaces of the multilayer wafer 10 in the stacking direction. However, the external electrodes 20a and 20b are separated from each other.
積層晶片10具有交替地積層有包含作為介電體而發揮功能之陶瓷材料之介電層11與包含賤金屬材料之內部電極層12的積層體之構成。各內部電極層12之端緣交替地露出於積層晶片10之設有外部電極20a之端面與設有外部電極20b之端面。藉此，各內部電極層12交替地導通於外部電極20a與外部電極20b。其結果為，積層陶瓷電容器100具有複數個介電層11介隔內部電極層12而積層之構成。又，於介電層11與內部電極層12之積層體中，於積層方向之最外層配置有內部電極層12，該積層體之上表面及下表面被覆蓋層13覆蓋。覆蓋層13以陶瓷材料為主成分。例如，覆蓋層13之材料與介電層11之陶瓷材料之主成分相同。The multilayer wafer 10 has a structure in which a dielectric layer 11 including a ceramic material functioning as a dielectric body and an internal electrode layer 12 including a base metal material are alternately stacked. An end edge of each internal electrode layer 12 is alternately exposed on an end surface on which the external electrode 20 a is provided and an end surface on which the external electrode 20 b is provided in the multilayer wafer 10. Thereby, each of the internal electrode layers 12 is alternately conducted to the external electrodes 20a and 20b. As a result, the multilayer ceramic capacitor 100 has a structure in which a plurality of dielectric layers 11 are laminated with the internal electrode layer 12 interposed therebetween. In the multilayer body of the dielectric layer 11 and the internal electrode layer 12, an internal electrode layer 12 is disposed at the outermost layer in the stacking direction, and the upper and lower surfaces of the multilayer body are covered with a cover layer 13. The cover layer 13 is mainly composed of a ceramic material. For example, the material of the cover layer 13 is the same as that of the ceramic material of the dielectric layer 11.
積層陶瓷電容器100之尺寸例如為長度0.2 mm、寬度0.125 mm、高度0.125 mm，或長度0.4 mm、寬度0.2 mm、高度0.2 mm，或長度0.6 mm、寬度0.3 mm、高度0.3 mm，或長度1.0 mm、寬度0.5 mm、高度0.5 mm，或長度3.2 mm、寬度1.6 mm、高度1.6 mm，或長度4.5 mm、寬度3.2 mm、高度2.5 mm，但並不限定於該等尺寸。The dimensions of the multilayer ceramic capacitor 100 are, for example, length 0.2 mm, width 0.125 mm, height 0.125 mm, or length 0.4 mm, width 0.2 mm, height 0.2 mm, or length 0.6 mm, width 0.3 mm, height 0.3 mm, or length 1.0 mm. , Width 0.5 mm, height 0.5 mm, or length 3.2 mm, width 1.6 mm, height 1.6 mm, or length 4.5 mm, width 3.2 mm, height 2.5 mm, but not limited to these dimensions.
內部電極層12以Ni(鎳)、Cu(銅)、Sn(錫)等賤金屬為主成分。作為內部電極層12，可使用Pt(鉑)、Pd(鈀)、Ag(銀)、Au(金)等貴金屬或包含該等之合金。The internal electrode layer 12 mainly includes base metals such as Ni (nickel), Cu (copper), and Sn (tin). As the internal electrode layer 12, a noble metal such as Pt (platinum), Pd (palladium), Ag (silver), Au (gold), or an alloy containing these can be used.
介電層11例如以陶瓷材料為主成分，該陶瓷材料以通式ABO3 所表示之鈣鈦礦結構為主相。再者，該鈣鈦礦結構包含脫離化學計量組成之ABO3- α 。例如，作為該陶瓷材料，可使用BaTiO3 (鈦酸鋇)、CaZrO3 (鋯酸鈣)、CaTiO3 (鈦酸鈣)、SrTiO3 (鈦酸鍶)、形成鈣鈦礦結構之Ba1-x-y Cax Sry Ti1-z Zrz O3 (0≦x≦1、0≦y≦1、0≦z≦1)等。The dielectric layer 11 includes, for example, a ceramic material as a main component, and the ceramic material has a perovskite structure represented by the general formula ABO 3 as a main phase. Furthermore, the perovskite structure contains ABO 3- α which is out of stoichiometric composition. For example, as the ceramic material, BaTiO 3 (barium titanate), CaZrO 3 (calcium zirconate), CaTiO 3 (calcium titanate), SrTiO 3 (strontium titanate), and Ba 1- to form a perovskite structure can be used. xy Ca x Sr y Ti 1-z Zr z O 3 (0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1), and the like.
為了使積層陶瓷電容器100小型大容量化，期望使介電層11薄膜化。然而，若欲使介電層11薄膜化，則有因絕緣破壞等導致壽命特性劣化，可靠性降低之虞。In order to reduce the size and capacity of the multilayer ceramic capacitor 100, it is desirable to reduce the thickness of the dielectric layer 11. However, if the dielectric layer 11 is to be formed into a thin film, the lifetime characteristics may be deteriorated due to insulation breakdown and the like, and reliability may be reduced.
此處，對可靠性降低進行說明。介電層11例如以使用以通式ABO3 所表示之鈣鈦礦結構為主相之陶瓷原料粉末之陶瓷材料為主成分，故而燒成時暴露於還原氛圍，從而導致ABO3 產生氧缺陷。使用積層陶瓷電容器100時，對介電層11反覆施加電壓。此時由於氧缺陷移動，導致勢壘被破壞。即，鈣鈦礦結構中之氧缺陷成為介電層11之可靠性降低之主要原因。Here, the decrease in reliability will be described. The dielectric layer 11 is, for example, a ceramic material using a ceramic raw material powder having a perovskite structure represented by the general formula ABO 3 as a main phase. Therefore, the dielectric layer 11 is exposed to a reducing atmosphere during firing, thereby causing oxygen defects in the ABO 3 . When the multilayer ceramic capacitor 100 is used, a voltage is repeatedly applied to the dielectric layer 11. At this time, the oxygen barrier moves and the potential barrier is destroyed. That is, the oxygen defect in the perovskite structure becomes the main cause of the decrease in the reliability of the dielectric layer 11.
因此，於本實施形態中，作為供體而發揮功能之元素包含(置換固溶)於鈣鈦礦結構之B部位。例如，作為作為供體而發揮功能之元素，可列舉：Mo(鉬)、Nb(鈮)、Ta(鉭)、W(鎢)等。藉由作為供體而發揮功能之元素置換固溶於B部位，可抑制鈣鈦礦結構中之氧缺陷。藉此，可延長介電層11之壽命，提昇可靠性。Therefore, in this embodiment, the element that functions as a donor is contained (displaced into a solid solution) at the B site of the perovskite structure. For example, as an element which functions as a donor, Mo (molybdenum), Nb (niobium), Ta (tantalum), W (tungsten), etc. are mentioned. By displacing an element that functions as a donor to dissolve in the B site, oxygen deficiency in the perovskite structure can be suppressed. Thereby, the life of the dielectric layer 11 can be extended, and the reliability can be improved.
於B部位中，若作為供體而發揮功能之元素過少，則有無法充分抑制氧缺陷之虞。因此，較佳為於B部位中，對作為供體而發揮功能之元素之置換固溶量設置下限。例如，於B部位中，於將B部位之主成分元素設為100 atm%之情形時，作為供體而發揮功能之元素較佳為置換固溶0.05 atm%以上，更佳為置換固溶0.1 atm%以上。In the B site, if there are too few elements functioning as a donor, there is a possibility that oxygen deficiency cannot be sufficiently suppressed. Therefore, it is preferable to set a lower limit for the replacement solid solution amount of the element that functions as a donor in the B site. For example, in the case where the main component element of the B site is set to 100 atm%, the element that functions as a donor is preferably replaced with a solid solution of 0.05 atm% or more, and more preferably replaced with a solid solution of 0.1 atm% or more.
另一方面，於B部位中，若作為供體而發揮功能之元素過多，則有產生絕緣性降低之不良情況之虞。因此，較佳為於B部位中，對作為供體而發揮功能之元素之置換固溶量設置上限。例如，於B部位中，作為供體而發揮功能之元素較佳為置換固溶0.3 atm%以下，更佳為置換固溶0.25 atm%以下。On the other hand, if there are too many elements that function as donors in the B site, there is a possibility that a defect such as a reduction in insulation may occur. Therefore, it is preferable to set an upper limit for the amount of replacement solid solution of the element that functions as a donor in the B site. For example, in the site B, it is preferable that the element functioning as a donor is 0.3 atm% or less, and more preferably 0.25 atm% or less.
其次，於還原氛圍下燒成以使用以鈣鈦礦結構為主相之陶瓷原料粉末之陶瓷材料為主成分之介電層11後，進行再氧化，藉此可進一步抑制氧缺陷。若再氧化時A部位及B部位兩者均包含(置換固溶)有稀土類元素，則可抑制燒成後之氧缺陷量。藉此，可於維持絕緣(IR：Insulation Resistance)特性之狀態下實現長壽命特性。其結果為，可實現較高之可靠性。因此，於本實施形態中，於A部位及B部位兩者均置換固溶有稀土類元素。Secondly, the dielectric layer 11 containing a ceramic material using a ceramic raw material powder having a perovskite structure as a main phase as a main component is fired in a reducing atmosphere, and then reoxidized, thereby further suppressing oxygen defects. When both the A site and the B site contain (replace solid solution) rare earth elements during reoxidation, the amount of oxygen defects after firing can be suppressed. Thereby, long-life characteristics can be realized while maintaining the insulation resistance (IR) characteristics. As a result, high reliability can be achieved. Therefore, in this embodiment, the rare-earth element is solid-displaced at both the A site and the B site.
若稀土類元素於A部位之置換固溶量(A部位固溶量)相對於稀土類元素於B部位之置換固溶量(B部位固溶量)過多，則有成為向鈣鈦礦添加過量供體之狀態之虞。於該情形時，有絕緣特性劣化之虞。另一方面，若B部位固溶量相對於A部位固溶量過多，則有成為向鈣鈦礦添加過量受體之狀態之虞。於該情形時，有氧缺陷量增大而壽命特性劣化之虞。因此，藉由將A部位固溶量與B部位固溶量之比設為1附近，可抑制燒成後之氧缺陷量，可獲得絕緣特性與壽命特性之平衡優異之高可靠性。具體而言，0.75≦(A部位固溶量/B部位固溶量)≦1.25。再者，就進一步抑制供體添加過量之狀態之觀點而言，較佳為(A部位固溶量/B部位固溶量)≦1.20，更佳為(A部位固溶量/B部位固溶量)≦1.10，進而較佳為(A部位固溶量/B部位固溶量)≦1.05。就進一步抑制受體添加過量之狀態之觀點而言，較佳為0.90≦(A部位固溶量/B部位固溶量)，更佳為0.95≦(A部位固溶量/B部位固溶量)。If the replacement solid solution amount of the rare earth element at the A site (the solid solution amount at the A site) is too much relative to the replacement solid solution amount of the rare earth element at the B site (the solid solution amount at the B site), there may be an excessive addition to the perovskite The state of the donor. In this case, there is a possibility that the insulation characteristics are deteriorated. On the other hand, if the amount of solid solution at the B site is too large relative to the amount of solid solution at the A site, there is a possibility that a state in which an excessive amount of acceptor is added to the perovskite may be obtained. In this case, the amount of aerobic defects may increase and the life characteristics may deteriorate. Therefore, by setting the ratio of the solid solution amount of the A site to the solid solution amount of the B site to be near 1, the amount of oxygen defects after firing can be suppressed, and high reliability with excellent balance of insulation characteristics and life characteristics can be obtained. Specifically, 0.75 ≦ (the amount of solid solution at the A site / the amount of solid solution at the B site) ≦ 1.25. Furthermore, from the viewpoint of further suppressing the state of excessive addition of the donor, (the amount of solid solution at the site A / the amount of solid solution at the site B) ≦ 1.20, and more preferably Amount) ≦ 1.10, and more preferably (A-part solid solution amount / B-part solid solution amount) ≦ 1.05. From the viewpoint of further suppressing the state of excessive addition of the receptor, it is preferably 0.90 ≦ (amount of solid solution in part A / amount of solid solution in part B), and more preferably 0.95 ≦ (amount of solid solution in part A / solid solution in part B) ).
再者，於A部位及B部位中，若稀土類元素過少，則有無法充分抑制燒成後之氧缺陷量之虞。因此，較佳為於A部位及B部位中，對稀土類元素之置換固溶量之合計設置下限。例如，於A部位及B部位中，稀土類元素之置換固溶量之合計較佳為0.2 atm%以上，更佳為0.3 atm%以上。此處之atm%係指將陶瓷原料粉末之ABO3 之B部位元素設為100 atm%之情形時之濃度。Furthermore, if there are too few rare earth elements in the A site and the B site, the amount of oxygen defects after firing may not be sufficiently suppressed. Therefore, it is preferable to set a lower limit to the total amount of the replacement solid solution amount of the rare earth element in the A site and the B site. For example, in the A site and the B site, the total amount of the replacement solid solution amount of the rare earth element is preferably 0.2 atm% or more, and more preferably 0.3 atm% or more. Here, atm% means the concentration when the element at the B site of ABO 3 of the ceramic raw material powder is 100 atm%.
另一方面，於A部位及B部位中，若稀土類元素過多，則有產生晶粒之正方晶性降低，介電常數降低之不良情況之虞。因此，較佳為於A部位及B部位中，對稀土類元素之置換固溶量之合計設置上限。例如，於A部位及B部位中，稀土類元素之置換固溶量之合計較佳為1.0 atm%以下，更佳為0.9 atm%以下。On the other hand, if there are too many rare earth elements in the A site and the B site, there may be a disadvantage that the tetragonality of the crystal grains decreases and the dielectric constant decreases. Therefore, it is preferable to set an upper limit to the total amount of the replacement solid solution amount of the rare earth element in the A site and the B site. For example, in the A site and the B site, the total amount of the replacement solid solution amount of the rare earth element is preferably 1.0 atm% or less, and more preferably 0.9 atm% or less.
作為稀土類元素，可使用Y(釔)、La(鑭)、Ce(鈰)、Pr(鐠)、Nd(釹)、Pm(鉕)、Sm(釤)、Eu(銪)、Gd(釓)、Tb(鋱)、Dy(鏑)、Ho(鈥)、Er(鉺)、Tm(銩)、Yb(鐿)等。再者，A部位之離子半徑與B部位之離子半徑不同。為了使稀土類元素平衡良好地置換固溶於A部位及B部位，較佳為稀土類元素之離子半徑為A部位之離子半徑與B部位之離子半徑之間。例如，根據表1，於使用BaTiO3
作為鈣鈦礦之情形時，較佳為使La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Y、Er、Tm、Yb等置換固溶。再者，表1之出典為「R. D. Shannon, Acta Crystallogr., A32, 751 (1976)」。
[表1]
[Table 1]
再者，離子半徑相對較大之La、Ce、Pr、Nd、Pm、Sm、Eu、Gd等有置換固溶於A部位之傾向。另一方面，離子半徑相對較小之Er、Tm、Yb等有置換固溶於B部位之傾向。因此，於使La、Ce、Pr、Nd、Pm、Sm、Eu、Gd等置換固溶之情形時，較佳為使Er、Tm、Yb等亦一併置換固溶。Furthermore, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, etc., which have relatively large ionic radii, tend to displace and dissolve in the A site. On the other hand, Er, Tm, Yb, etc., which have relatively small ionic radii, tend to displace into solid solution at the B site. Therefore, when La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, etc. are replaced by solid solution, it is preferable that Er, Tm, Yb, etc. are also replaced by solid solution.
又，於B部位置換固溶有作為供體而發揮功能之元素，於A部位及B部位兩者均置換固溶有稀土類元素之狀態之鈣鈦礦(Am BO3 )中，若「m」之值過小，則產生絕緣性降低之不良情況。因此，較佳為對「m」之值設置下限。具體而言，較佳為m≧1.002。另一方面，若「m」之值過大，則產生燒結性惡化之不良情況。因此，較佳為對「m」之值設置上限。具體而言，較佳為m≦1.010。In addition, at the B site, solid-dissolving elements that function as donors are replaced, and at the sites A and B, the perovskite (A m BO 3 ) in the state where the rare earth elements are solid-dissolved is replaced by " If the value of "m" is too small, a defect such as a reduction in insulation occurs. Therefore, it is preferable to set a lower limit for the value of "m". Specifically, it is preferably m ≧ 1.002. On the other hand, if the value of "m" is too large, there is a problem that the sinterability is deteriorated. Therefore, it is preferable to set an upper limit to the value of "m". Specifically, it is preferably m ≦ 1.010.
又，介電層11中之主成分陶瓷之平均結晶粒徑較佳為80 nm～300 nm，更佳為80 nm～200 nm。若主成分陶瓷之平均結晶粒徑較小，則有介電常數降低，無法獲得所期望之靜電電容之虞，另一方面，若平均結晶粒徑較大，於如介電層11為1.0 μm以下之厚度之情形時，則有作為氧缺陷之移動勢壘而起作用之晶界面積減少，因此導致壽命特性降低之虞。The average crystal grain size of the main component ceramic in the dielectric layer 11 is preferably 80 nm to 300 nm, and more preferably 80 nm to 200 nm. If the average crystal grain size of the main component ceramics is small, the dielectric constant may be lowered, and the desired capacitance may not be obtained. On the other hand, if the average crystal grain size is large, for example, the dielectric layer 11 is 1.0 μm. In the case of the following thickness, the interfacial area of the crystal which functions as a moving barrier of an oxygen defect is reduced, and thus the life characteristics may be reduced.
再者，亦可藉由使介電層11厚膜化而獲得高可靠性。然而，於該情形時，會使積層陶瓷電容器100大型化。因此，本實施形態對小型積層陶瓷電容器100特別發揮效果。例如，本實施形態於介電層11之厚度為1.0 μm以下之薄層之積層陶瓷電容器中特別有效。進而，若將介電層11之厚度設為0.4 μm以下，則可製成更小型且高可靠性之積層陶瓷電容器。又，介電層11之厚度更佳為0.2 μm以上，以不使絕緣電阻值降低。Furthermore, a high reliability can also be obtained by thickening the dielectric layer 11. However, in this case, the multilayer ceramic capacitor 100 is increased in size. Therefore, the present embodiment is particularly effective for the small multilayer ceramic capacitor 100. For example, this embodiment is particularly effective for a multilayer ceramic capacitor having a thin layer with a thickness of the dielectric layer 11 of 1.0 μm or less. Furthermore, if the thickness of the dielectric layer 11 is 0.4 μm or less, a multilayer ceramic capacitor having a smaller size and higher reliability can be manufactured. The thickness of the dielectric layer 11 is more preferably 0.2 μm or more so as not to reduce the insulation resistance value.
繼而，對積層陶瓷電容器100之製造方法進行說明。圖2係例示積層陶瓷電容器100之製造方法之流程之圖。Next, a method for manufacturing the multilayer ceramic capacitor 100 will be described. FIG. 2 is a diagram illustrating a flow of a manufacturing method of the multilayer ceramic capacitor 100.
(原料粉末製作步驟)
首先，準備陶瓷原料粉末，該陶瓷原料粉末以通式ABO3
所表示之鈣鈦礦結構為主相，於B部位置換固溶有作為供體而發揮功能之元素，於A部位及B部位兩者均置換固溶有稀土類元素。使用該陶瓷原料粉末之陶瓷材料係介電層11之主成分。作為該陶瓷原料粉末之合成方法，先前已知各種方法，例如已知固相合成法、溶膠-凝膠合成法、水熱合成法等。再者，於將稀土類元素於A部位之置換固溶量設為A部位固溶量，將稀土類元素於B部位之置換固溶量設為B部位固溶量之情形時，設為0.75≦(A部位固溶量/B部位固溶量)≦1.25。作為一例，對固相合成法進行說明。首先，將TiO2
粉末及BaCO3
粉末與純水等溶劑及分散劑等混合而製作漿料。其次，將對乙酸中溶解有稀土類之溶液進行中和處理而得者添加於該漿料並進行混練、分散處理。再者，亦可進而向漿料中添加鉬化合物之粉末並於該鉬離子化或錯合物化之狀態下進行混練、分散處理。混練、分散使用珠磨機等進行20小時～30小時。其次，將該漿料乾燥而獲得原材料。將該原材料於800℃～1150℃下進行第1次煅燒，獲得陶瓷原料粉末。(Material powder production steps)
First, a ceramic raw material powder is prepared. The ceramic raw material powder has a perovskite structure represented by the general formula ABO 3 as a main phase, and a solution-soluble element serving as a donor is replaced at the B site. All are replaced with solid-solution rare earth elements. The ceramic material using the ceramic raw material powder is a main component of the dielectric layer 11. As a method for synthesizing the ceramic raw material powder, various methods have been previously known, such as a solid-phase synthesis method, a sol-gel synthesis method, a hydrothermal synthesis method, and the like. Further, when the replacement solid solution amount of the rare earth element at the A site is the solid solution amount of the A site, and the replacement solid solution amount of the rare earth element at the B site is the solid solution amount of the B site, it is 0.75. ≦ (Solution amount at site A / Solution amount at site B) ≦ 1.25. As an example, a solid-phase synthesis method will be described. First, TiO 2 powder and BaCO 3 powder are mixed with a solvent such as pure water, a dispersant, and the like to prepare a slurry. Next, the solution obtained by neutralizing a rare earth dissolved in acetic acid is added to the slurry and kneaded and dispersed. Further, a powder of a molybdenum compound may be further added to the slurry, and the molybdenum may be kneaded and dispersed in a state where the molybdenum is ionized or complexed. Kneading and dispersion are performed for 20 to 30 hours using a bead mill or the like. Next, this slurry is dried to obtain a raw material. This raw material is calcined for the first time at 800 ° C to 1150 ° C to obtain a ceramic raw material powder.
根據目的向所獲得之陶瓷原料粉末中添加特定之添加化合物。作為添加化合物，可列舉：Mg(鎂)、Mn(錳)、V(釩)、Cr(鉻)之氧化物；以及Co(鈷)、Ni、Li(鋰)、B(硼)、Na(鈉)、K(鉀)及Si(矽)之氧化物；或者玻璃。A specific additive compound is added to the obtained ceramic raw material powder according to the purpose. Examples of the additional compounds include oxides of Mg (magnesium), Mn (manganese), V (vanadium), and Cr (chromium); and Co (cobalt), Ni, Li (lithium), B (boron), and Na ( Sodium), K (potassium) and Si (silicon) oxides; or glass.
例如，向陶瓷原料粉末中混合包含添加化合物之化合物並於820～1150℃下進行第2次煅燒。繼而，進行濕式混合並進行乾燥及粉碎，製備陶瓷材料。例如，就介電層11之薄層化之觀點而言，陶瓷材料之平均粒徑較佳為50～150 nm。例如，對於以上述方式獲得之陶瓷材料，可視需要進行粉碎處理而調節粒徑，或者藉由與分級處理組合而使粒徑整齊。藉由以上步驟，可獲得作為介電層之主成分之陶瓷材料。For example, a compound containing an additive compound is mixed with the ceramic raw material powder, and the second firing is performed at 820 to 1150 ° C. Next, a ceramic material is prepared by wet-mixing, drying and pulverizing. For example, from the viewpoint of thinning the dielectric layer 11, the average particle diameter of the ceramic material is preferably 50 to 150 nm. For example, the ceramic material obtained in the above manner may be subjected to a pulverization treatment to adjust the particle diameter as required, or may be made to have a uniform particle diameter by being combined with a classification treatment. Through the above steps, a ceramic material as a main component of the dielectric layer can be obtained.
(積層步驟)
其次，向所獲得之陶瓷材料中添加聚乙烯醇縮丁醛(PVB)樹脂等黏合劑、乙醇、甲苯等有機溶劑及塑化劑並進行濕式混合。使用所獲得之漿料，例如藉由模嘴塗佈法或刮刀法，於基材上塗佈例如厚度為3 μm～10 μm之帶狀之介電坯片並進行乾燥。(Lamination step)
Next, to the obtained ceramic material, a binder such as polyvinyl butyral (PVB) resin, an organic solvent such as ethanol, toluene, and a plasticizer are added and wet-mixed. Using the obtained slurry, for example, a tape-shaped dielectric green sheet having a thickness of 3 μm to 10 μm is coated on a substrate by a die coating method or a doctor blade method and dried.
其次，藉由網版印刷、凹版印刷等將包含有機黏合劑之內部電極形成用之金屬導電膏印刷至介電坯片之表面，藉此於極性不同之一對外部電極配置交替地引出之內部電極層圖案。於金屬導電膏中添加陶瓷粒子作為相同材料。陶瓷粒子之主成分並無特別限定，較佳為與介電層11之主成分陶瓷相同。例如，可使平均粒徑為50 nm以下之BaTiO3 均勻地分散。Secondly, a metal conductive paste for forming an internal electrode containing an organic binder is printed on the surface of the dielectric blank by screen printing, gravure printing, etc., thereby arranging the interior of the external electrodes alternately in one of the different polarities. Electrode layer pattern. Ceramic particles are added to the metal conductive paste as the same material. The main component of the ceramic particles is not particularly limited, and it is preferably the same as the main component ceramic of the dielectric layer 11. For example, BaTiO 3 having an average particle diameter of 50 nm or less can be uniformly dispersed.
其後，將印刷有內部電極層圖案之介電坯片沖裁成特定大小，將沖裁所得之介電坯片，於剝離基材之狀態下，以內部電極層12與介電層11交替之方式，且以內部電極層12於介電層11之長度方向兩個端面端緣交替地露出而交替地引出至極性不同之一對外部電極20a、20b之方式，積層特定層數(例如100～500層)。將用於形成覆蓋層13之覆蓋片壓接於所積層之介電坯片之上下，並切割成特定晶片尺寸(例如1.0 mm×0.5 mm)。Thereafter, the dielectric green sheet printed with the internal electrode layer pattern is punched to a specific size, and the punched dielectric green sheet is alternated with the internal electrode layer 12 and the dielectric layer 11 in a state where the substrate is peeled off. In this way, and in a manner that the two end edges of the internal electrode layer 12 in the longitudinal direction of the dielectric layer 11 are alternately exposed and alternately drawn to one pair of external electrodes 20a and 20b with different polarities, a specific number of layers (for example, 100 ~ 500 layers). The cover sheet for forming the cover layer 13 is crimped on and under the laminated dielectric green sheet, and cut into a specific wafer size (for example, 1.0 mm × 0.5 mm).
將所獲得之陶瓷積層體於N2 氛圍中脫黏合劑後，自陶瓷積層體之兩個端面向各側面塗佈金屬膏，並進行乾燥，該金屬膏包含含有外部電極20a、20b之主成分金屬之金屬填料、相同材料、黏合劑、溶劑等，且成為外部電極20a、20b之基底層。After the obtained ceramic laminate is debonded in an N 2 atmosphere, a metal paste is applied from both ends of the ceramic laminate to each side and dried, and the metal paste contains the main components containing the external electrodes 20a and 20b. A metal filler, the same material, an adhesive, a solvent, etc. of the metal, and become a base layer of the external electrodes 20a, 20b.
(燒成步驟)
將如此獲得之成形體於250～500℃之N2
氛圍中進行脫黏合劑處理後，於氧分壓為10-5
～10-8
atm之還原氛圍中以1100～1300℃燒成10分鐘～2小時，藉此成形體中之粒子燒結而發生晶粒生長。如此，獲得燒結體。(Baking step)
The thus-obtained formed body is subjected to debinding treatment in an N 2 atmosphere at 250 to 500 ° C, and then fired at 1100 to 1300 ° C for 10 minutes in a reducing atmosphere having an oxygen partial pressure of 10 -5 to 10 -8 atm ~ For 2 hours, the particles in the formed body were sintered to cause grain growth. In this way, a sintered body was obtained.
(再氧化處理步驟)
其後，於N2
氛圍圍中以600℃～1000℃進行再氧化處理。藉由該步驟抑制氧缺陷。(Reoxidation treatment step)
Thereafter, a reoxidation treatment is performed at 600 ° C. to 1000 ° C. in a N 2 atmosphere. This step suppresses oxygen deficiency.
(外部電極形成步驟)
其後，於外部電極20a、20b之基底層上，藉由鍍覆處理進行Cu、Ni、Sn等之金屬塗覆。(External electrode formation step)
Thereafter, on the base layers of the external electrodes 20a and 20b, metal coating such as Cu, Ni, Sn, etc. is performed by a plating process.
根據本實施形態之製造方法，於原料粉末製作步驟中所使用之陶瓷原料粉末中，作為供體而發揮功能之元素置換固溶於鈣鈦礦結構之B部位，因此於燒成步驟中可抑制鈣鈦礦結構中之氧缺陷。藉此，可延長介電層11之壽命，提昇可靠性。又，稀土類元素置換固溶於A部位及B部位，因此可抑制燒成後之氧缺陷量。藉此，可於維持絕緣特性之狀態下實現長壽命特性。其結果為，可實現較高之可靠性。又，藉由設為0.75≦(A部位固溶量/B部位固溶量)≦1.25，可抑制燒成後之氧缺陷量，可獲得絕緣特性與壽命特性之平衡優異之高可靠性。According to the manufacturing method of this embodiment, in the ceramic raw material powder used in the raw material powder manufacturing step, an element that functions as a donor is replaced with a solid solution in the B part of the perovskite structure, so it can be suppressed in the firing step. Oxygen deficiency in perovskite structure. Thereby, the life of the dielectric layer 11 can be extended, and the reliability can be improved. In addition, since the rare-earth element substitution is solid-dissolved in the A site and the B site, the amount of oxygen defects after firing can be suppressed. Thereby, long-life characteristics can be realized while maintaining the insulation characteristics. As a result, high reliability can be achieved. In addition, by setting 0.75 ≦ (solid solution amount in part A / solid solution amount in part B) ≦ 1.25, the amount of oxygen defects after firing can be suppressed, and high reliability with excellent balance of insulation characteristics and life characteristics can be obtained.
再者，就進一步抑制供體添加過量之狀態之觀點而言，較佳為(A部位固溶量/B部位固溶量)≦1.20，更佳為(A部位固溶量/B部位固溶量)≦1.10，進而較佳為(A部位固溶量/B部位固溶量)≦1.05。就進一步抑制受體添加過量之狀態之觀點而言，較佳為0.90≦(A部位固溶量/B部位固溶量)，更佳為0.95≦(A部位固溶量/B部位固溶量)。Furthermore, from the viewpoint of further suppressing the state of excessive addition of the donor, (the amount of solid solution at the A site / the amount of solid solution at the B site) ≦ 1.20, and more preferably (the amount of solid solution at the A site / the solution at the B site) Amount) ≦ 1.10, and more preferably (A-part solid solution amount / B-part solid solution amount) ≦ 1.05. From the viewpoint of further suppressing the state of excessive addition of the receptor, it is preferably 0.90 ≦ (amount of solid solution in part A / amount of solid solution in part B), and more preferably 0.95 ≦ (amount of solid solution in part A / solid solution in part B) ).
於B部位中，若作為供體而發揮功能之元素過少，則有無法充分抑制氧缺陷之虞。因此，較佳為於B部位中，對作為供體而發揮功能之元素之置換固溶量設置下限。例如，於B部位中，於將B部位之主成分元素設為100 atm%之情形時，作為供體而發揮功能之元素較佳為置換固溶0.05 atm%以上，更佳為置換固溶0.1 atm%以上。In the B site, if there are too few elements functioning as a donor, there is a possibility that oxygen deficiency cannot be sufficiently suppressed. Therefore, it is preferable to set a lower limit for the replacement solid solution amount of the element that functions as a donor in the B site. For example, in the case where the main component element of the B site is set to 100 atm%, the element that functions as a donor is preferably replaced with a solid solution of 0.05 atm% or more, and more preferably replaced with a solid solution of 0.1 atm% or more.
另一方面，於B部位中，若作為供體而發揮功能之元素過多，則有產生絕緣性降低之不良情況之虞。因此，較佳為於B部位中，對作為供體而發揮功能之元素之置換固溶量設置上限。例如，於B部位中，作為供體而發揮功能之元素較佳為置換固溶0.3 atm%以下，更佳為置換固溶0.25 atm%以下。On the other hand, if there are too many elements that function as donors in the B site, there is a possibility that a defect such as a reduction in insulation may occur. Therefore, it is preferable to set an upper limit for the amount of replacement solid solution of the element that functions as a donor in the B site. For example, in the site B, it is preferable that the element functioning as a donor is 0.3 atm% or less, and more preferably 0.25 atm% or less.
再者，於A部位及B部位中，若稀土類元素過少，則有無法充分抑制燒成後之氧缺陷量之虞。因此，較佳為於A部位及B部位中，對稀土類元素之置換固溶量之合計設置下限。例如，於A部位及B部位中，稀土類元素之置換固溶量之合計較佳為0.2 atm%以上，更佳為0.3 atm%以上。此處之atm%係指將陶瓷原料粉末之ABO3 之B部位元素設為100 atm%之情形時之濃度。Furthermore, if there are too few rare earth elements in the A site and the B site, the amount of oxygen defects after firing may not be sufficiently suppressed. Therefore, it is preferable to set a lower limit to the total amount of the replacement solid solution amount of the rare earth element in the A site and the B site. For example, in the A site and the B site, the total amount of the replacement solid solution amount of the rare earth element is preferably 0.2 atm% or more, and more preferably 0.3 atm% or more. Here, atm% means the concentration when the element at the B site of ABO 3 of the ceramic raw material powder is 100 atm%.
另一方面，於A部位及B部位中，若稀土類元素過多，則有產生晶粒之正方晶性降低，介電常數降低之不良情況之虞。因此，較佳為於A部位及B部位中，對稀土類元素之置換固溶量之合計設置上限。例如，於A部位及B部位中，稀土類元素之置換固溶量之合計較佳為1.0 atm%以下，更佳為0.9 atm%以下。On the other hand, if there are too many rare earth elements in the A site and the B site, there may be a disadvantage that the tetragonality of the crystal grains decreases and the dielectric constant decreases. Therefore, it is preferable to set an upper limit to the total amount of the replacement solid solution amount of the rare earth element in the A site and the B site. For example, in the A site and the B site, the total amount of the replacement solid solution amount of the rare earth element is preferably 1.0 atm% or less, and more preferably 0.9 atm% or less.
作為稀土類元素，可使用Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb等。再者，A部位之離子半徑與B部位之離子半徑不同。為了使稀土類元素平衡良好地置換固溶於A部位及B部位，較佳為稀土類元素之離子半徑為A部位之離子半徑與B部位之離子半徑之間。例如，根據表1，於使用BaTiO3 作為鈣鈦礦之情形時，較佳為使La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Y、Er、Tm、Yb等置換固溶。As the rare earth element, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and the like can be used. Furthermore, the ionic radius of the A site is different from the ionic radius of the B site. In order to replace the rare-earth element with a solid solution at the A and B sites in a well-balanced manner, it is preferable that the ionic radius of the rare-earth element is between the ionic radius of the A site and the ionic radius of the B site. For example, according to Table 1, when using BaTiO 3 as a perovskite, it is preferable to use La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Tm, Yb, etc. replace solid solution.
再者，離子半徑相對較大之La、Ce、Pr、Nd、Pm、Sm、Eu、Gd等有置換固溶於A部位之傾向。另一方面，離子半徑相對較小之Er、Tm、Yb等有置換固溶於B部位之傾向。因此，於使La、Ce、Pr、Nd、Pm、Sm、Eu、Gd等置換固溶之情形時，較佳為亦使Er、Tm、Yb等一併置換固溶。Furthermore, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, etc., which have relatively large ionic radii, tend to displace and dissolve in the A site. On the other hand, Er, Tm, Yb, etc., which have relatively small ionic radii, tend to displace into solid solution at the B site. Therefore, in the case where La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, etc. are replaced by solid solution, it is preferable that Er, Tm, Yb, etc. are also replaced by solid solution.
又，於B部位置換固溶有作為供體而發揮功能之元素，於A部位及B部位兩者均置換固溶有稀土類元素之狀態之鈣鈦礦(Am
BO3
)中，若「m」之值過小，則產生絕緣性降低之不良情況。因此，較佳為對「m」之值設置下限。具體而言，較佳為m≧1.002。另一方面，若「m」之值過大，則產生燒結性惡化之不良情況。因此，較佳為對「m」之值設置上限。具體而言，較佳為m≦1.010。
[實施例]In addition, at the B site, solid-dissolving elements that function as donors are replaced, and at the sites A and B, the perovskite (A m BO 3 ) in the state where the rare earth elements are solid-dissolved is replaced by " If the value of "m" is too small, a defect such as a reduction in insulation occurs. Therefore, it is preferable to set a lower limit for the value of "m". Specifically, it is preferably m ≧ 1.002. On the other hand, if the value of "m" is too large, there is a problem that the sinterability is deteriorated. Therefore, it is preferable to set an upper limit to the value of "m". Specifically, it is preferably m ≦ 1.010.
[Example]
以下，製作實施形態之積層陶瓷電容器，並對特性進行調查。Hereinafter, a multilayer ceramic capacitor of an embodiment is manufactured and its characteristics are investigated.
首先，準備於B部位置換固溶有作為供體而發揮功能之元素，於A部位及B部位兩者均置換固溶有稀土類元素之BaTiO3 之陶瓷原料粉末。平均粒徑為150 nm。於實施例1～11及比較例1～9之任一者中，於B部位中Ti為100 atm%之情形時，使Mo置換固溶0.2 atm%。First, a ceramic raw material powder in which the rare earth element BaTiO 3 is solid-dissolved is replaced at the B-site with elements that function as donors. The average particle size was 150 nm. In any of Examples 1 to 11 and Comparative Examples 1 to 9, when Ti was 100 atm% in the B site, Mo was replaced by a solid solution of 0.2 atm%.
實施例1～2中，使用以0.2 atm%之Ho為稀土類元素進行置換固溶而得之陶瓷原料粉末，其後以Ho2 O3 之形式添加相當於0.8 atm%之Ho。實施例3～7中，使用以0.5 atm%之Ho為稀土類元素進行置換固溶而得之陶瓷原料粉末，其後以Ho2 O3 之形式添加相當於0.5 atm%之Ho。實施例8中，分別使用以0.25 atm%之Gd及Yb為稀土類元素進行置換固溶而得之陶瓷原料粉末，其後以Gd2 O3 之形式添加相當於0.25 atm%之Gd，以Yb2 O3 之形式添加相當於0.25 atm%之Yb。實施例9～11中，使用以1.0 atm%之Ho為稀土類元素進行置換固溶而得之陶瓷原料粉末。比較例1中，不使稀土類元素置換固溶於陶瓷原料粉末，以Ho2 O3 之形式添加相當於1.0 atm%之Ho。比較例2中，使用置換固溶有0.2 atm%之Ho之陶瓷原料粉末，其後以Ho2 O3 之形式添加相當於0.8 atm%之Ho。比較例3～5中，使用置換固溶有0.5 atm%之Ho之陶瓷原料粉末，其後以Ho2 O3 之形式添加相當於0.5 atm%之Ho。比較例6中，分別使用以0.2 atm%及0.3 atm%之Gd及Yb為稀土類元素進行置換固溶而得之陶瓷原料粉末，其後以Gd2 O3 之形式添加相當於0.2 atm%之Gd，以Yb2 O3 之形式添加相當於0.3 atm%之Yb。比較例7中，分別使用以0.3 atm%及0.2 atm%之Gd及Yb為稀土類元素進行置換固溶而得之陶瓷原料粉末，其後以Gd2 O3 之形式添加相當於0.3 atm%之Gd，以Yb2 O3 之形式添加相當於0.2 atm%之Yb。比較例8～9中，使用以1.0 atm%之Ho為稀土類元素進行置換固溶而得之陶瓷原料粉末。該段落中之atm%係指將陶瓷原料粉末之ABO3 之B部位設為100 atm%之情形時之濃度。In Examples 1 and 2, a ceramic raw material powder obtained by replacing and solid-solving with 0.2 atm% of Ho as a rare earth element was used, and then Ho equivalent to 0.8 atm% was added in the form of Ho 2 O 3 . In Examples 3 to 7, a ceramic raw material powder obtained by replacing and solid-solving with 0.5 atm% of Ho as a rare earth element was used, and then Ho equivalent to 0.5 atm% was added in the form of Ho 2 O 3 . In Example 8, ceramic raw material powders obtained by replacing solid solution with 0.25 atm% of Gd and Yb as rare earth elements were added, and then Gd equivalent to 0.25 atm% of Gd was added as Gd 2 O 3 , and Yb The addition of 2 O 3 is equivalent to 0.25 atm% of Yb. In Examples 9 to 11, ceramic raw material powders obtained by replacing and solid-solving with 1.0 atm% of Ho as a rare earth element were used. In Comparative Example 1, the rare earth element was not replaced with a solid solution in the ceramic raw material powder, and Ho equivalent to 1.0 atm% was added as Ho 2 O 3 . In Comparative Example 2, a ceramic raw material powder in which 0.2 atm% of Ho was solid-displaced was used, and then Ho equivalent to 0.8 atm% was added as Ho 2 O 3 . In Comparative Examples 3 to 5, a ceramic raw material powder in which 0.5 atm% of Ho was solid-displaced was used, and then Ho equivalent to 0.5 atm% was added as Ho 2 O 3 . In Comparative Example 6, a ceramic raw material powder obtained by replacing and solid-solving with 0.2 atm% and 0.3 atm% of Gd and Yb as rare earth elements, respectively, was added in the form of Gd 2 O 3 equivalent to 0.2 atm%. Gd, adding Yb equivalent to 0.3 atm% in the form of Yb 2 O 3 . In Comparative Example 7, ceramic raw material powders obtained by substituting and replacing solid solutions with Gd and Yb of 0.3 atm% and 0.2 atm% as rare earth elements, respectively, were added in the form of Gd 2 O 3 equivalent to 0.3 atm%. Gd, adding Yb equivalent to 0.2 atm% in the form of Yb 2 O 3 . In Comparative Examples 8 to 9, ceramic raw material powders obtained by replacing and dissolving Ho with 1.0 atm% of Ho as a rare earth element were used. The atm% in this paragraph refers to the concentration when the B part of ABO 3 of the ceramic raw material powder is set to 100 atm%.
實施例1中，(A部位固溶量/B部位固溶量)為0.95。實施例2中，(A部位固溶量/B部位固溶量)為1.10。實施例3中，(A部位固溶量/B部位固溶量)為0.75。實施例4中，(A部位固溶量/B部位固溶量)為0.95。實施例5中，(A部位固溶量/B部位固溶量)為1.00。實施例6中，(A部位固溶量/B部位固溶量)為1.05。實施例7中，(A部位固溶量/B部位固溶量)為1.25。實施例8中，(A部位固溶量/B部位固溶量)為1.10。實施例9中，(A部位固溶量/B部位固溶量)為0.75。實施例10中，(A部位固溶量/B部位固溶量)為1.03。實施例11中，(A部位固溶量/B部位固溶量)為1.20。比較例2中，(A部位固溶量/B部位固溶量)為1.32。比較例3中，(A部位固溶量/B部位固溶量)為0.50。比較例4中，(A部位固溶量/B部位固溶量)為1.35。比較例5中，(A部位固溶量/B部位固溶量)為1.50。比較例6中，(A部位固溶量/B部位固溶量)為0.70。比較例7中，(A部位固溶量/B部位固溶量)為1.50。比較例8中，(A部位固溶量/B部位固溶量)為0.66。實施例9中，(A部位固溶量/B部位固溶量)為1.30。In Example 1, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 0.95. In Example 2, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 1.10. In Example 3, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 0.75. In Example 4, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 0.95. In Example 5, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 1.00. In Example 6, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 1.05. In Example 7, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 1.25. In Example 8, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 1.10. In Example 9, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 0.75. In Example 10, (the amount of solid solution at the site A / the amount of solid solution at the site B) was 1.03. In Example 11, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 1.20. In Comparative Example 2, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 1.32. In Comparative Example 3, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 0.50. In Comparative Example 4, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 1.35. In Comparative Example 5, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 1.50. In Comparative Example 6, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 0.70. In Comparative Example 7, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 1.50. In Comparative Example 8, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 0.66. In Example 9, (the amount of solid solution at the A site / the amount of solid solution at the B site) was 1.30.
再者，關於置換固溶量，對藉由Ar離子將陶瓷原料粉末蝕刻加工為半球狀而得之試樣，使用穿透式電子顯微鏡(TEM)，藉由能量分散型螢光X射線分析法(EDS)進行測定。關於(A部位固溶量/B部位固溶量)，對同樣地加工之試樣，藉由高角散射環形暗場掃描穿透顯微鏡法(HADDF-STEM)進行測定。Regarding the amount of replacement solid solution, a sample obtained by etching and processing a ceramic raw material powder into a hemispherical shape using Ar ions was subjected to an energy dispersive fluorescent X-ray analysis method using a transmission electron microscope (TEM). (EDS). Regarding (the amount of solid solution at the A site / the amount of solid solution at the B site), a sample processed in the same manner was measured by a high-angle scattering annular dark-field scanning penetration microscope method (HADDF-STEM).
再者，於實施例1～11及比較例1～9之任一者中，於B部位置換固溶有Mo，於A部位及B部位之兩者均置換固溶有稀土類元素之狀態之Am BO3 中，將「m」之值設為1.002。In addition, in any of Examples 1 to 11 and Comparative Examples 1 to 9, Mo was replaced with a solid solution at the B site, and a state where a rare earth element was solid solution was replaced at both the A site and the B site. In A m BO 3 , the value of "m" is set to 1.002.
於陶瓷原料粉末中添加1.0 mol%之MgO作為添加劑，分別添加各0.05 mol%之MnO及V2 O5 作為添加劑，分別添加各1.0 mol%之SiO2 及BaCO3 作為燒結助劑。再者，該情形時之「mol%」係將陶瓷原料粉末之ABO3 設為100 mol%之情形時之數值。1.0 mol% of MgO is added to the ceramic raw material powder, 0.05 mol% of MnO and V 2 O 5 are added as additives, and 1.0 mol% of SiO 2 and BaCO 3 are added as sintering aids, respectively. The "mol%" in this case is a value when the ABO 3 of the ceramic raw material powder is 100 mol%.
將添加有添加劑及燒結助劑之陶瓷原料粉末藉由球磨機充分濕式混合粉碎，獲得陶瓷材料。於陶瓷材料中添加有機黏合劑及溶劑，藉由刮刀法製作介電坯片。將介電坯片之塗佈厚度設為0.8 μm，使用聚乙烯醇縮丁醛(PVB)等作為有機黏合劑，添加乙醇、甲苯酸等作為溶劑。另外，添加塑化劑等。其次，藉由行星型球磨機製作內部電極形成用導電膏，該內部電極形成用導電膏包含內部電極層12之主成分金屬(Ni)之粉末、相同材料(鈦酸鋇)、黏合劑(乙基纖維素)、溶劑、及視需要之其他助劑。The ceramic raw material powder added with the additive and the sintering aid is sufficiently wet-mixed and pulverized by a ball mill to obtain a ceramic material. An organic binder and a solvent are added to the ceramic material, and a dielectric green sheet is produced by a doctor blade method. The coating thickness of the dielectric green sheet was set to 0.8 μm, and polyvinyl butyral (PVB) or the like was used as an organic binder, and ethanol, toluic acid or the like was added as a solvent. In addition, a plasticizer is added. Next, a conductive paste for internal electrode formation was produced by a planetary ball mill, and the conductive paste for internal electrode formation contained powder of the main component metal (Ni) of the internal electrode layer 12, the same material (barium titanate), and a binder (ethyl Cellulose), solvents, and other additives as needed.
於介電片網版印刷內部電極形成用導電膏。將印刷有內部電極形成用導電膏之片材重疊250片，於其上下分別積層覆蓋片。其後，藉由熱壓接獲得陶瓷積層體，將其切割為特定形狀。將所獲得之陶瓷積層體於N2 氛圍中脫黏合劑後，自陶瓷積層體之兩個端面向各側面塗佈金屬膏，並進行乾燥，該金屬膏包含以Ni為主成分之金屬填料、相同材料、黏合劑、溶劑等，且成為外部電極20a、20b之基底層。其後，於還原氛圍中以1100℃～1300℃與陶瓷積層體同時燒成金屬膏10分鐘～2小時，獲得燒結體。A conductive paste for internal electrode formation is screen-printed on a dielectric sheet. The sheet on which the conductive paste for forming internal electrodes was printed was superposed on 250 sheets, and overlay sheets were stacked on top and bottom, respectively. Thereafter, a ceramic laminate is obtained by thermocompression bonding, and it is cut into a specific shape. After the obtained ceramic laminate is debonded in an N 2 atmosphere, a metal paste is applied from both ends of the ceramic laminate to each side and dried, and the metal paste includes a metal filler mainly composed of Ni, The same materials, adhesives, solvents, etc., and serve as a base layer for the external electrodes 20a, 20b. Thereafter, the metal paste is fired simultaneously with the ceramic laminate at a temperature of 1100 ° C to 1300 ° C in a reducing atmosphere for 10 minutes to 2 hours to obtain a sintered body.
所獲得之燒結體之形狀尺寸為長度0.6 mm、寬度0.3 mm、高度0.3 mm。將燒結體於N2 氛圍下以800℃之條件進行再氧化處理後，進行鍍覆處理而於外部電極20a、20b之基底層之表面形成Cu鍍覆層、Ni鍍覆層及Sn鍍覆層，藉此形成外部電極20a、20b，獲得積層陶瓷電容器100。The shape and size of the obtained sintered body were 0.6 mm in length, 0.3 mm in width, and 0.3 mm in height. The sintered body was subjected to reoxidation treatment at 800 ° C. in an N 2 atmosphere, and then subjected to a plating treatment to form a Cu plating layer, a Ni plating layer, and a Sn plating layer on the surface of the base layer of the external electrodes 20 a and 20 b. Thereby, the external electrodes 20a and 20b are formed, and the multilayer ceramic capacitor 100 is obtained.
(分析)
對實施例1～11及比較例1～9，分別製作20個樣品。對各樣品進行壽命特性試驗，測定平均壽命。再者，於壽命特性試驗中，於125℃下藉由10 V之直流電壓施加實施，藉由電流計測定洩漏電流值，將至絕緣破壞之時間設為壽命值。又，對各樣品進行絕緣電阻試驗，測定平均絕緣電阻。再者，於絕緣電阻試驗中，於室溫下藉由10 V之直流電壓施加實施，根據60秒後之電流值測定電阻。(analysis)
For Examples 1 to 11 and Comparative Examples 1 to 9, 20 samples were prepared. The life characteristics test was performed on each sample, and the average life was measured. In the life characteristic test, a DC voltage of 10 V was applied at 125 ° C., and a leakage current value was measured by a galvanometer. The time until the insulation failure was set as the life value. In addition, an insulation resistance test was performed on each sample to measure the average insulation resistance. In the insulation resistance test, a DC voltage of 10 V was applied at room temperature, and the resistance was measured based on the current value after 60 seconds.
於平均壽命為100 min以下之情形時，判定壽命特性為不合格「×」。於絕緣電阻為10 MΩ以下之情形時，判定絕緣特性為不合格「×」。於判定壽命特性及絕緣特性之任一者為不合格之情形時，判定可靠性為「不合格」。結果示於表2。
[表2]
[Table 2]
比較例1中，壽命特性、絕緣特性均判定為不合格。可認為其原因在於，由於使用未置換固溶稀土類元素之陶瓷原料粉末，故而導致無法充分置換固溶。比較例2、4、5、7、9中，判定壽命特性為合格，另一方面，判定絕緣特性為不合格。可認為其原因在於(A部位固溶量/B部位固溶量)超過1.25。比較例3、6、8中，判定絕緣特性為合格，另一方面，判定壽命特性為不合格。可認為其原因在於(A部位固溶量/B部位固溶量)低於0.75。In Comparative Example 1, both the life characteristics and the insulation characteristics were determined to be unacceptable. The reason for this is considered to be that the solid solution cannot be fully replaced due to the use of ceramic raw material powders that have not been replaced with the solid solution rare earth elements. In Comparative Examples 2, 4, 5, 7, and 9, the life characteristics were judged to be acceptable, while the insulation characteristics were judged to be unacceptable. The reason is considered to be that (the amount of solid solution at the A site / the amount of solid solution at the B site) exceeds 1.25. In Comparative Examples 3, 6, and 8, the insulation characteristics were judged to be acceptable, while the life characteristics were judged to be unacceptable. This is considered to be because (the amount of solid solution at the A site / the amount of solid solution at the B site) is less than 0.75.
相對於該等，於實施例1～11之任一者中，判定壽命特性及絕緣特性之兩者為合格。可認為其原因在於，於B部位置換固溶有作為供體而發揮功能之元素，於A部位及B部位之兩者均置換固溶有稀土類元素，(A部位固溶量/B部位固溶量)進入0.75以上且1.25以下之範圍。On the other hand, in any of Examples 1 to 11, it was determined that both the life characteristics and the insulation characteristics were acceptable. The reason for this is considered to be that the solid-dissolving element is replaced at the B site with the element functioning as a donor, and the rare-earth element is solid-displaced at both the A site and the B site. Solubility) is in the range of 0.75 or more and 1.25 or less.
再者，實施例4、5中，與實施例3相比，絕緣電阻及壽命特性更良好。可認為其原因在於(A部位固溶量/B部位固溶量)成為0.95以上。實施例2中，與實施例7相比，絕緣電阻及壽命特性良好。可認為其原因在於(A部位固溶量/B部位固溶量)成為1.10以下。實施例5、6中，與實施例2相比，絕緣電阻及壽命特性更良好。可認為其原因在於(A部位固溶量/B部位固溶量)成為1.05以下。實施例10中，與實施例9相比，壽命特性更良好。可認為其原因在於(A部位固溶量/B部位固溶量)成為0.95以上。又，實施例10中，與實施例11相比，壽命特性更良好。可認為其原因在於(A部位固溶量/B部位固溶量)成為1.05以下。In addition, in Examples 4 and 5, the insulation resistance and life characteristics were better than those in Example 3. The reason for this is considered to be that (the amount of solid solution at the A site / the amount of solid solution at the B site) is 0.95 or more. In Example 2, compared with Example 7, the insulation resistance and life characteristics were good. The reason for this is considered to be that (the amount of solid solution at the A site / the amount of solid solution at the B site) is 1.10 or less. In Examples 5 and 6, compared with Example 2, the insulation resistance and life characteristics were better. The reason for this is considered to be that (the amount of solid solution at the A site / the amount of solid solution at the B site) is 1.05 or less. In Example 10, compared with Example 9, the lifetime characteristics were better. The reason for this is considered to be that (the amount of solid solution at the A site / the amount of solid solution at the B site) is 0.95 or more. Moreover, in Example 10, compared with Example 11, the lifetime characteristics were more favorable. The reason for this is considered to be that (the amount of solid solution at the A site / the amount of solid solution at the B site) is 1.05 or less.
以上，對本發明之實施例進行詳細說明，但本發明並不限定於該特定實施例，於申請專利範圍所記載之本發明之主旨之範圍內，可進行各種變化、變更。The embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific embodiments, and various changes and modifications can be made within the scope of the gist of the present invention described in the patent application scope.
10‧‧‧積層晶片10‧‧‧Laminated Wafer
11‧‧‧介電層 11‧‧‧ Dielectric layer
12‧‧‧內部電極層 12‧‧‧ Internal electrode layer
13‧‧‧覆蓋層 13‧‧‧ Overlay
20a、20b‧‧‧外部電極 20a, 20b‧‧‧External electrode
100‧‧‧積層陶瓷電容器 100‧‧‧Multilayer Ceramic Capacitor
圖1係積層陶瓷電容器之局部剖面立體圖。Fig. 1 is a partial sectional perspective view of a multilayer ceramic capacitor.
圖2係例示積層陶瓷電容器之製造方法之流程之圖。 FIG. 2 is a flowchart illustrating a manufacturing method of a multilayer ceramic capacitor.
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| TWI235391B (en) * | 2002-10-17 | 2005-07-01 | Murata Manufacturing Co | Dielectric ceramic and method for preparation thereof, and monolithic ceramic capacitor |
| JP2005145791A (en) * | 2003-11-19 | 2005-06-09 | Tdk Corp | Electronic components, dielectric porcelain composition, and method for manufacturing the same |
| JP5108779B2 (en) | 2006-10-27 | 2012-12-26 | 京セラ株式会社 | Dielectric porcelain and capacitor |
| JP5803694B2 (en) | 2012-01-24 | 2015-11-04 | Tdk株式会社 | Dielectric ceramic composition and ceramic electronic component |
| KR20140100218A (en) * | 2013-02-06 | 2014-08-14 | 삼성전기주식회사 | Dielectric composition and multi-layer ceramic electronic parts fabricated by using the same |
| CN104098329B (en) * | 2013-04-11 | 2016-06-01 | 华新科技股份有限公司 | Dielectric ceramic material composition and comprise the monolithic ceramic capacitor of described composition |
| JP6533429B2 (en) | 2015-07-28 | 2019-06-19 | 太陽誘電株式会社 | Multilayer ceramic capacitor |
| KR102166127B1 (en) * | 2015-12-28 | 2020-10-15 | 삼성전기주식회사 | Dielectric composition and multilayer ceramic capacitor comprising the same |
| JP6571048B2 (en) * | 2016-06-24 | 2019-09-04 | 太陽誘電株式会社 | Multilayer ceramic capacitor, ceramic powder, and manufacturing method thereof |
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2018
- 2018-11-26 JP JP2018220281A patent/JP7338963B2/en active Active
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2019
- 2019-03-06 CN CN201910167134.5A patent/CN110233048B/en active Active
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113327768A (en) * | 2020-02-28 | 2021-08-31 | 太阳诱电株式会社 | Ceramic electronic component and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2023021997A (en) | 2023-02-14 |
| TWI784140B (en) | 2022-11-21 |
| CN110233048A (en) | 2019-09-13 |
| KR20190106699A (en) | 2019-09-18 |
| CN110233048B (en) | 2022-05-13 |
| JP2019161217A (en) | 2019-09-19 |
| JP7525974B2 (en) | 2024-07-31 |
| JP7338963B2 (en) | 2023-09-05 |
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