TWI573775B - Ceramic capacitor dielectric material - Google Patents

Ceramic capacitor dielectric material Download PDF

Info

Publication number
TWI573775B
TWI573775B TW104123019A TW104123019A TWI573775B TW I573775 B TWI573775 B TW I573775B TW 104123019 A TW104123019 A TW 104123019A TW 104123019 A TW104123019 A TW 104123019A TW I573775 B TWI573775 B TW I573775B
Authority
TW
Taiwan
Prior art keywords
ceramic capacitor
dielectric material
capacitor dielectric
present
added
Prior art date
Application number
TW104123019A
Other languages
English (en)
Other versions
TW201704187A (zh
Inventor
Xi-Fu Wang
Jun-Wei Zhang
Jue-Wei WENG
Jian-Hua Li
yuan-zheng Lai
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed filed Critical
Priority to TW104123019A priority Critical patent/TWI573775B/zh
Priority to CN201510793454.3A priority patent/CN106348753B/zh
Priority to US14/956,046 priority patent/US9963393B2/en
Priority to JP2016008778A priority patent/JP6334580B2/ja
Publication of TW201704187A publication Critical patent/TW201704187A/zh
Application granted granted Critical
Publication of TWI573775B publication Critical patent/TWI573775B/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/49—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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or 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
    • C04B35/622—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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • 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
    • C04B35/626—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
    • C04B35/63—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 using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/638—Removal thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
    • H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G4/1245—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates containing also 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides 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
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides 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
    • C04B2235/3224—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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides 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
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • 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
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C04B2235/3234—Titanates, not containing zirconia
    • C04B2235/3236—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
    • 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
    • C04B2235/3241—Chromium oxides, chromates, 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
    • C04B2235/3231—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
    • C04B2235/3248—Zirconates or hafnates, e.g. zircon
    • 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
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, 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
    • C04B2235/3258—Tungsten oxides, tungstates, 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • 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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, 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
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
    • 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
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates 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
    • C04B2235/34—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
    • C04B2235/02—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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • 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
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • 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
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/762—Cubic symmetry, e.g. beta-SiC
    • 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
    • C04B2235/95—Products characterised by their size, e.g. microceramics

Description

陶瓷電容介電材料
本發明是有關一種陶瓷電容介電材料，特別是一種使用複合材料的觀點，以製成符合EIA之X7T介電特性之陶瓷電容介電材料。
鈦酸鋇（BaTiO 3）系列電子陶瓷是近數十年來發展起來的一類新型功能陶瓷。鈦酸鋇（BaTiO 3）是一種結晶質陶瓷，在常溫下亦具有不對稱結構。鈦離子稍微偏離單位晶胞的中心，致使該晶體成為正方晶系結構並具有永久極化。此種晶體特性以及它對作用電場的迅速反應導致鈦酸鋇和類似的材料具有極高的介電常數。
而鈦酸鋇常應用於各種陶瓷電容器以及動態隨機存取記憶體的產業，並主要作為電容器、啟動器、記憶體、場效應電晶體、電子濾波器、熱敏電阻、邏輯電路等的原材料。近年來，移動電子設備的小型化使得多層陶瓷電容器（MLCC）逐漸向低成本、小型化、大容量的方向發展。介電溫度穩定性高的MLCC類型介電材料有NP0、X7R、X7T等，由美國電子工業協會電容器規範中提到，X7T於溫度範圍-55℃~ 125℃之間，電容變化率必須在+22%到-33%之間。
以鈦酸鋇（BaTiO 3）來看，雖然具有較高的介電常數，但鈦酸鋇的介電常數在-90°C、0°C和125°C時波動很大，以此特性來看，將無法滿足EIA之X7T介電特性，故如此特性也限制了鈦酸鋇（BaTiO 3）來看的應用範圍。
由美國引證案US 20110164346及US 8450230中可知，主要是利用形成核殼結構來達到X7T規範，當藉由BaTiO 3形成核殼結構，可以用來抑制居禮點的介電峰值，以穩定介電性質對溫度的穩定性，而常見形成方式為藉由摻雜元素後經過高溫燒結的過程中會產生擴散，但由於擴散深度並不完全故會在晶粒中產生濃度梯度的差異而形成核殼結構。
而美國引證案US 20110164346及US 8450230中提到介電陶瓷組合物包括至少一種BaTiO 3、(Ba, Ca)TiO 3、(Ba, Sr)TiO 3、(Ba, Ca, Sr)TiO 3、稀土類元素的氧化物和複合化合物（包含Ba. 9 to 13 mol的電介質組合物）；而介電陶瓷組合物為殼核結構，其中可分為擴散相及非擴散相，而殼核結構的控制主要是利用添加不同mol%之BaZrO 3或是稀土元素R或是控制升降溫速率，以此來調整核殼結構中之擴散相面積(S2)、非擴散相面積(S1)及稀土元素之平均濃度(C)，藉由S1、S2、C的控制來達到TDK所要求的S1:S2=20:80 to 30:70以及4.8 ≦ S2xC≦5.8。
但由於BaTiO 3對溫度的穩定性會大大影響其介電特性，在0°C ~130°C為正方相結構，並於接近居禮點溫度時其介電性質的變化劇烈，為了克服上述問題，則能夠以複合材料的觀點，將BaTiO 3、BaZrO 3及SrTiO 3為主體、並混合至少一種化合物，而本發明為了穩定溫度所造成之影響，故添加BaZrO 3使居禮點溫度降至室溫以下，形成穩定的立方相結構，由於相結構的穩定能提升介電性質對溫度的穩定性，除此之外，更會至少選擇一種稀土元素做摻雜，以藉此穩定溫度對電容的影響及電場對溫度的影響，以製成符合EIA之X7T介電特性之陶瓷電容介電材料，因此本發明應為一最佳解決方案。
本發明係關於一種陶瓷電容介電材料，係以複合材料的觀點，將BaTiO 3、BaZrO 3及SrTiO 3為主體、並混合至少一種或一種以上的化合物，並於混合之化合物以一種稀土元素做摻雜，藉此穩定溫度對電容的影響及電場對電容的影響，以製成符合EIA之X7T介電特性之陶瓷電容介電材料。
本發明係關於一種陶瓷電容介電材料，為了穩定溫度所造成之影響，故添加BaZrO 3使居禮點溫度降至室溫以下，形成穩定的立方相結構，由於相結構的穩定能提升介電性質對溫度的穩定性。
可達成上述陶瓷電容介電材料，該陶瓷電容介電材料的組成以BaTiO 3、BaZrO 3及SrTiO 3為主體，並混合MgCO 3、SiO 2及至少一種或一種以上的化合物，該化合物係選自於過渡元素或稀土元素，其中，BaTiO 3之添加量係為40至80mol%、BaZrO 3之添加量係為20至40mol%、SrTiO 3之添加量係為小於或等於20mol%。
更具體的說，所述MgCO 3之添加量係為2至6 mol %。
更具體的說，所述SiO 2之添加量係為小於或等於2mol%。
更具體的說，所述稀土元素係為La 2O 3、CeO 2、Pr 6O 11、Nd 2O 3、Pm 2O 3、Sm 2O 3、Eu 2O 3、Gd 2O 3、Dy 2O 3、Ho 2O 3、Er 2O 3、Tm 2O 3、Yb 2O 3，而上述該些稀土元素之添加量係為0.5~10mol%。
更具體的說，所述過渡元素係為Nb 2O 5、WO 3、Ta 2O 5、CoCO 3、CuO、MnCO 3、Cr 2O 3、TiO 2、ZrO 2 、Sc 2O 3、NiO、ZnO，而上述該些過渡元素之添加量係為0.5~10mol%。
更具體的說，所述主體混合至少一種化合物後，則能夠進行燒結製程，而該燒結製程之燒結溫度必須能夠使陶瓷電容燒結達到緻密化。
更具體的說，所述製備完成之陶瓷電容介電材料之室溫介電損失小於0.5%。
更具體的說，所述製備完成之陶瓷電容介電材料於溫度-55至125℃之間時，電容變化率是介於+22%到-33%之間。
有關於本發明其他技術內容、特點與功效，在以下配合參考圖式之較佳實施例的詳細說明中，將可清楚的呈現。
請參閱第1圖，為本發明陶瓷電容介電材料之製備流程示意圖，由圖中可知，其步驟為： (1)     將(1-x-y)BaTiO 3-xBaZrO 3-ySrTiO 3添加摻雜物，依照不同比例倒入有氧化鋯磨球及酒精之球磨罐中混和球磨24小時後取出烘乾。其中0.2≤x≤0.4，0.0 ≤ y ≤0.2 101； (2)     接著均勻研磨粉末，添加適量黏結劑PVA進行造粒，再以60 mesh篩網進行過篩102； (3)     將過篩後之粉末進行單軸成型，以1 ton壓力持續30秒製作直徑約90 mm、厚度1 mm之坯體103； (4)     再以550℃，持溫4小時，升溫速率5℃/min之條件進行黏結劑燒除（脫脂）104； (5)     將脫脂後之樣品在還原氣氛下以不同溫度持溫2個小時，升溫速率5℃/min進行高溫燒結105； (6)     完成燒結後於大氣下以900℃進行退火熱處理，升溫速率5℃/min，持溫時間2小時106； (7)     接著用阿基米德密度測量，並挑選緻密之樣品進行XRD及SEM分析。最後將樣品雙面拋光後均勻塗佈電極膏，烘乾後用800℃不持溫條件下進行電極燒附，使用燒附電極之樣品進行介電性質之測量及分析107。
而本發明之陶瓷電容介電材料的組成以鈦酸鋇（BaTiO 3）、鋯酸鋇（BaZrO 3）及鈦酸鍶（SrTiO 3）為主體，並混合MgCO 3、SiO 2及至少一種或一種以上的化合物，該化合物係選自於過渡元素或稀土元素，其中，BaTiO 3之添加量（組成陶瓷電容介電材料之配比）係為40至80mol%、BaZrO 3之添加量（組成陶瓷電容介電材料之配比）係為20至40mol%、SrTiO 3之添加量（組成陶瓷電容介電材料之配比）係為小於或等於20mol%；其中鋯酸鋇（BaZrO 3）能夠以BaZrO 3的元素粉末進行添加，或是由不同元素合成為BaZrO 3（例如BaO+ZrO 2），因此以不同形式合成為成BaZrO 3、並進行添加且添加之比例如同本發明所揭露之比例範圍，皆為本發明所保護之範圍。而除了鋯酸鋇（BaZrO 3）之外，鈦酸鋇（BaTiO 3）、鈦酸鍶（SrTiO 3）、碳酸鎂（MgCO 3）、二氧化矽（SiO 2）與所添加之過渡元素或稀土元素，皆如同鋯酸鋇（BaZrO 3）一樣，不論是什麼形式合成為BaTiO 3、SrTiO 3、MgCO 3、SiO 2、過渡元素、稀土元素、並進行添加且添加之比例如同本發明所揭露之比例範圍，皆為本發明所保護之範圍。
另外，以 BaTiO 3、BaZrO 3及SrTiO 3為主體，並混合MgCO 3、SiO 2及至少一種或一種以上的化合物所製成陶瓷電容介電材料，若最後形成之陶瓷電容介電材料具有上述提到之任何元素（BaTiO 3、SrTiO 3、MgCO 3、SiO 2、過渡元素、稀土元素）之配比，皆為本發明所保護之範圍。
除此之外，所添加之化合物除了過渡元素或稀土元素之外，亦能夠添加鈦酸鎂（MgTiO 3），其添加量（組成陶瓷電容介電材料之配比）係為0至6mol%（莫耳百分比能夠為0、0.5、1、1.5、2、2.5、3、3.5、4、4.5、5、5.5或6 mol %）
其中，鈦酸鋇（BaTiO 3）之添加量係為40至80mol%（能夠為45、50、55、60、65、70、75或80mol%）；鋯酸鋇（BaZrO 3）之添加量係為20至40%（能夠為20、25、30、35或40mol%）；鈦酸鍶（SrTiO 3）之添加量係小於或等於20mol%（能夠為0、5、10、15、20mol%）。
其中，混合之碳酸鎂（MgCO 3）之添加量（組成陶瓷電容介電材料之配比）係為2至6%（能夠為2、2.5、3、3.5、4、4.5、5、5.5或6mol%），添加MgCO 3是為了調整A/B ratio，因為BaTiO 3在還原氣氛下燒結時會形成氧空位，基於化學平衡反應，會使介電材料容易半導體化，故添加BaTiO 3使其Mg2+離子取代Ti4+離子，以離子補償的方式降低半導體化之現象，提高可靠度。
其中，混合之二氧化矽（SiO 2）之添加量（組成陶瓷電容介電材料之配比）係小於或等於2%（能夠為0、0.5、1、1.5或2mol%），添加SiO 2是作為助燒劑幫助陶瓷體燒結，可以降低燒結溫度同時提升燒結緻密性，由於燒結體本身會有孔洞存在，孔洞越多則減少之單位體積內的電偶極矩也越多，會影響整體的介電性質，另外若使其他物質進入孔隙中也會影響介電特性，故添加SiO 2來做改善，另一優點為藉由添加SiO 2也能提高介電材料之電阻係數。
為了穩定溫度所造成之影響，故添加BaZrO 3使居禮點溫度降至室溫以下，形成穩定的立方相結構，由於相結構的穩定能提升介電性質對溫度的穩定性，本發明相較於美國引證案US 20110164346及US 8450230，其差異如第2圖所示，其主體的部份，本發明有添加BaZrO 3的添加量最少為20ml%，最多為40mol%，但引證案主體的部份其添加BaZrO 3的添加量少於14mol%（最多加到14mol%），而除了BaZrO 3的添加量有明顯差異之外，由於X7T最主要的特性在於直流偏壓特性的穩定度，故本發明著重於此特性上之改良（本發明之直流偏壓特性明顯比引證案優秀），並同時符合X7T規範之要求，雖然在介電常數上較低於引證案，但本發明可在實際產品開發上進行調整來拉高介電常數之數值；
而本發明之電極的選擇係為Base-Metal Electrode（BME，卑金屬電極）由於MLCC追求更小型化及堆疊層數目的增加，故在電極的上所花費的成本也逐漸提升，此成本比重約為產品的三成~四成，故在電極的選擇上也須做為成本考量之一。相較於成本較高的NME（Noble Metal Electrolde，貴金屬電極）其使用的材料為Ag/Pd，本發明選擇的是使用成本較低的BME，其使用的材料為Ni/Cu，以此來製成MLCC。由於BME所使用之Ni/Cu在高溫下容易氧化，所以必須在還原氣氛下進行共燒製程。
而本發明為了要使介電特性能符合X7T規範，故在摻雜的化合物中至少選擇一種稀土元素做摻雜，藉此穩定溫度對電容的影響及電場對溫度的影響，而能夠使用的稀土元素係為La 2O 3、CeO 2、Pr 6O 11、Nd 2O 3、Pm 2O 3、Sm 2O 3、Eu 2O 3、Gd 2O 3、Dy 2O 3、Ho 2O 3、Er 2O 3、Tm 2O 3、Yb 2O 3，其中，上述該些稀土元素之添加量能夠介於0.5至10 mol%，以氧化鈥（Ho 2O 3）舉例來說，其添加量係介於0.5至10 mol%（添加量能夠為0.5、1、1.5、2、2.5、3、3.5、4、4.5、5、5.5、6、6.5、7、7.5、8、8.5、9、9.5或10 mol%），而其他稀土元素之添加量亦如氧化鈥（Ho 2O 3）所述相同，故不重覆贅述。
而除了稀土元素之外，更能夠添加過渡元素，而能夠使用的過渡元素係為Nb 2O 5、WO 3、Ta 2O 5、CoCO 3、CuO、MnCO 3、Cr 2O 3、TiO 2、ZrO 2、Sc 2O 3、NiO、ZnO，其中，添加量能夠介於0.5至10 mol%，以五氧化二鈮（Nb 2O 5）舉例來說，其添加量係介於0.5至10 mol%（添加量能夠為0.5、1、1.5、2、2.5、3、3.5、4、4.5、5、5.5、6、6.5、7、7.5、8、8.5、9、9.5或10 mol%），而其他過渡元素之添加量亦如氧化鈥五氧化二鈮（Nb 2O 5）所述相同，故不重覆贅述。
請參考第3A圖至第3D圖，本發明共做了22組的實驗組，而不同的實驗組共有不同的配比，而22組的實驗組的配比僅為參考，並不僅限於僅能應用如此配比，而22組的實驗組中並未添加五氧化二鈮（Nb 2O 5），但於實際上的應用中，亦能夠添加五氧化二鈮（Nb 2O 5）進行實施。
將使用燒附電極之22組的實驗組之樣品進行介電性質之測量及分析後，如第4A圖及第4C圖中可知，更測量得到22組的實驗組之介電常數（specific  Permittivity）、試片從125℃到-55℃的電容比上室溫的電容（Temp. Characteristic X7T）、室溫之介電損失率（Dielectric Loss at 25℃）、電阻率（Resistivity）、在2.5 kV/mm的電容損失率（Capacitance Change at 2.5kV/mm[%]），而22組的實驗組中，其中NO.4、NO.18、NO.19、NO.22的實驗組是可以得到符合X7T之TCC規範，且在直流偏壓的損失率都在1.5%上下。由於X7T算是特化的陶瓷電容編號，主要的應用範圍就是在高強度電場下希望電容損失率能越小越好，因此本發明不只TCC曲線進入X7T範圍，在直流偏壓亦有良好表現；另外，NO.20、NO.21、NO.22的實驗組是針對有進入到X7T規範之NO.18進行BaTiO 3與BaZrO 3比例上的調整，藉此了解在摻雜物的添加量固定時，調整BaTiO 3與BaZrO 3比例會對性質產生怎樣的影響。
而第5A圖至第5D圖，是TCC（125到-55℃的電容比上室溫的電容比率）與溫度的相對示意圖，由於美國電子工業協會電容器規範中提到，X7T於溫度範圍-55℃~ 125℃之間，電容變化率必須在+22%到-33%之間，由圖中可知，NO.4、NO.18、NO.19、NO.22的實驗組中，TCC都有進入範圍內，因此符合X7T之TCC規範。另外，以NO.18為對照組時可發現，當BaTiO 3含量越多時（即NO.20、NO.21），我們的TCC曲線會開始偏離X7T要求規範，且我們的直流偏壓特性會變差，但介電常數有一個明顯的提升；當BaTiO 3含量越少時（即NO.22），我們的TCC曲線會更進入X7T要求規範，且我們的直流偏壓特性會變好，其介電常數有一個小幅度的下降。
而第6A圖至第6D圖，是介電損失率與不同溫度的相對示意圖，當介電損失越高時，電容在儲存能量的表現會不佳，可能是以光、熱方式散失。因此在損失方面亦是越低越好，而本發明22組的實驗組之介電損失率皆偏低，尤其是介電損失（室溫）這方面，所得之數據皆在0.5%以下。由NO.18、NO.20、NO.21、NO.22的實驗組可得知，雖然我們改變了BaTiO 3與BaZrO 3比例，但對於介電損失來說並無明顯的差異，可以推測可能有效抑制介電損失最主要原因來自於添加稀土元素(R)之影響。
而第7A~7F圖中，將部份的實驗組於不同直流偏壓與電容損失以圖面表示，而本發明主要是要得知2.5 kV/mm的電容損失率，由於直流偏壓在外加電場越高情況下，是希望損失率越低，因此在高強度電場下則是希望電容損失率能越小越好；而搭配第3A~3C圖中可知，本發明在直流偏壓亦有良好表現，除此之外，當BaTiO 3含量越多時（即NO.20、NO.21），其介電常數有一個明顯的提升，而當BaTiO 3含量越少時（即NO.22），其介電常數有一個小幅度的下降，雖然如此，但仍進入我們X7T的規範。
另外，將NO.18進行MLCC的製備為樣品並進行量測後，將量測結果與具殼核結構之市售產品做一個性質上的比較，其介電性質分析結果數據示意圖、TCC與溫度的相對示意圖、電容損失率分析示意圖分別如第8A圖、第8B圖及第8C圖所示，由第8A圖中可知比較後之數據資料，再由第8B圖可知，在TCC曲線上NO.18 Bulk與成品MLCC幾乎是重疊的，也都有進入X7T規範要求，如此也確認了本發明進行MLCC製備的可行性；
再由第8C圖可知，雖然具殼核結構之市售產品其對於溫度的穩定性較優於我們、且介電常數也比我們高，但從第8C圖中可知，本發明NO.18所製成的MLCC具有非常優異的直流偏壓特性，其穩定度高出市售產品很多，故本發明有利於產品的應用上，而室溫時的介電損失與電阻係數兩者都是差不多的。
本發明所提供之陶瓷電容介電材料，與其他習用技術相互比較時，其優點如下： 1.         本發明能夠以複合材料的觀點，將BaTiO 3、BaZrO 3及SrTiO 3為主體、並混合MgCO 3、SiO 2及至少一種或一種以上的化合物，該化合物係選自於過渡元素或稀土元素，以製成符合EIA之X7T介電特性之陶瓷電容介電材料。 2.         本發明之陶瓷電容介電材料能夠符合X7T於溫度範圍-55℃~ 125℃之間，電容變化率必須在+22%到-33%之間的規範，且於不同溫度得到之介電損失率皆偏低（低於0.5%），而介電常數大於350。 3.         本發明之陶瓷電容介電材料之電阻係數在室溫時能到~10 12[Ω-cm]，而在125℃時能到能達到~10 11[Ω-cm]。 4.         由於直流偏壓在外加電場越高情況下，是希望損失率越低，因此在高強度電場下則是希望電容損失率能越小越好，而本發明之陶瓷電容介電材料在直流偏壓下的電容變化率亦有良好表現。
本發明已透過上述之實施例揭露如上，然其並非用以限定本發明，任何熟悉此一技術領域具有通常知識者，在瞭解本發明前述的技術特徵及實施例，並在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，因此本發明之專利保護範圍須視本說明書所附之請求項所界定者為準。
<TABLE border="1" borderColor="#000000" width="_0001"><TBODY><tr><td> 無 </td><td>   </td></tr></TBODY></TABLE>
[第1圖]係本發明陶瓷電容介電材料之製備流程示意圖。        [第2圖]係本發明陶瓷電容介電材料之特性與引證案比較示意圖。        [第3A圖]係本發明陶瓷電容介電材料之不同實驗組之配比莫耳比數據示意圖。        [第3B圖]係本發明陶瓷電容介電材料之不同實驗組之配比莫耳比數據示意圖。        [第3C圖] 係本發明陶瓷電容介電材料之不同實驗組之配比莫耳比數據示意圖。        [第3D圖] 係本發明陶瓷電容介電材料之不同實驗組之配比莫耳比數據示意圖。        [第4A圖]係本發明陶瓷電容介電材料之不同實驗組之介電性質分析結果數據示意圖。        [第4B圖]係本發明陶瓷電容介電材料之不同實驗組之介電性質分析結果數據示意圖。        [第4C圖]係本發明陶瓷電容介電材料之不同實驗組之介電性質分析結果數據示意圖。        [第5A圖]係本發明陶瓷電容介電材料之不同實驗組之TCC與溫度的相對示意圖。        [第5B圖]係本發明陶瓷電容介電材料之不同實驗組之TCC與溫度的相對示意圖。        [第5C圖]係本發明陶瓷電容介電材料之不同實驗組之TCC與溫度的相對示意圖。        [第5D圖]係本發明陶瓷電容介電材料之不同實驗組之TCC與溫度的相對示意圖。        [第6A圖]係本發明陶瓷電容介電材料之不同實驗組之介電損失率與溫度的相對示意圖。        [第6B圖]係本發明陶瓷電容介電材料之不同實驗組之介電損失率與溫度的相對示意圖。        [第6C圖]係本發明陶瓷電容介電材料之不同實驗組之介電損失率與溫度的相對示意圖。        [第6D圖]係本發明陶瓷電容介電材料之不同實驗組之介電損失率與溫度的相對示意圖。        [第7A圖]係本發明陶瓷電容介電材料之不同實驗組之電容損失率分析示意圖。        [第7B圖]係本發明陶瓷電容介電材料之不同實驗組之電容損失率分析示意圖。        [第7C圖]係本發明陶瓷電容介電材料之不同實驗組之電容損失率分析示意圖。        [第7D圖]係本發明陶瓷電容介電材料之不同實驗組之電容損失率分析示意圖。        [第7E圖]係本發明陶瓷電容介電材料之不同實驗組之電容損失率分析示意圖。        [第7F圖]係本發明陶瓷電容介電材料之不同實驗組之電容損失率分析示意圖。        [第8A圖]係本發明陶瓷電容介電材料之MLCC製備樣品與具殼核結構之市售產品比較之介電性質分析結果數據示意圖。        [第8B圖]係本發明陶瓷電容介電材料之MLCC製備樣品與具殼核結構之市售產品比較之TCC與溫度的相對示意圖。        [第8C圖]係本發明陶瓷電容介電材料之MLCC製備樣品與具殼核結構之市售產品比較之電容損失率分析示意圖。
<TABLE border="1" borderColor="#000000" width="_0002"><TBODY><tr><td>      無 </td><td>   </td></tr></TBODY></TABLE>

Claims (7)

  1. 一種陶瓷電容介電材料，該陶瓷電容介電材料的組成以BaTiO 3、BaZrO 3及SrTiO 3為主體，並混合MgCO 3、SiO 2及至少一種或一種以上的化合物，該化合物係選自於過渡元素或稀土元素，其中，BaTiO 3之添加量係為40至80mol%、BaZrO 3之添加量係為20至40mol%、SrTiO 3之添加量係小於或等於20mol%。
  2. 如請求項1所述之陶瓷電容介電材料，其中MgCO 3之添加量係為2至6mol%。
  3. 如請求項1所述之陶瓷電容介電材料，其中SiO 2之添加量係小於或等於2mol%。
  4. 如請求項1所述之陶瓷電容介電材料，其中稀土元素係為La 2O 3、CeO 2、Pr 6O 11、Nd 2O 3、Pm 2O 3、Sm 2O 3、Eu 2O 3、Gd 2O 3、Dy 2O 3、Ho 2O 3、Er 2O 3、Tm 2O 3、Yb 2O 3。
  5. 如請求項1所述之陶瓷電容介電材料，其中過渡元素係為Nb 2O 5、WO 3、Ta 2O 5、CoCO 3、CuO、MnCO 3、Cr 2O 3、TiO 2、ZrO 2、Sc 2O 3、NiO、ZnO。
  6. 如請求項1所述之陶瓷電容介電材料，其中製備完成之陶瓷電容介電材料之室溫介電損失小於0.5%。
  7. 如請求項1所述之陶瓷電容介電材料，其中製備完成之陶瓷電容介電材料於溫度-55至125℃之間時，電容變化率是介於+22%到-33%之間。
TW104123019A 2015-07-16 2015-07-16 Ceramic capacitor dielectric material TWI573775B (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
TW104123019A TWI573775B (zh) 2015-07-16 2015-07-16 Ceramic capacitor dielectric material
CN201510793454.3A CN106348753B (zh) 2015-07-16 2015-11-18 陶瓷电容介电材料
US14/956,046 US9963393B2 (en) 2015-07-16 2015-12-01 Ceramic capacitor dielectric material
JP2016008778A JP6334580B2 (ja) 2015-07-16 2016-01-20 セラミックコンデンサ誘電体材料

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
TW104123019A TWI573775B (zh) 2015-07-16 2015-07-16 Ceramic capacitor dielectric material

Publications (2)

Publication Number Publication Date
TW201704187A TW201704187A (zh) 2017-02-01
TWI573775B true TWI573775B (zh) 2017-03-11

Family

ID=57774782

Family Applications (1)

Application Number Title Priority Date Filing Date
TW104123019A TWI573775B (zh) 2015-07-16 2015-07-16 Ceramic capacitor dielectric material

Country Status (4)

Country Link
US (1) US9963393B2 (zh)
JP (1) JP6334580B2 (zh)
CN (1) CN106348753B (zh)
TW (1) TWI573775B (zh)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107226697A (zh) * 2017-06-01 2017-10-03 合肥尚强电气科技有限公司 一种环保高压陶瓷电容器介质材料及其制备方法
CN111869326B (zh) 2017-12-21 2023-09-26 保土谷化学工业株式会社 有机电致发光元件及其制造方法
CN110233047A (zh) * 2019-07-03 2019-09-13 华中科技大学 一种高储能密度电介质材料的制备方法
CN112645708B (zh) * 2020-12-24 2022-07-15 福建火炬电子科技股份有限公司 一种抗还原bme瓷介电容器及电容器用陶瓷材料
TWI776343B (zh) * 2020-12-31 2022-09-01 華新科技股份有限公司 陶瓷組成物、陶瓷燒結體、電容與電容製法
CN114591079B (zh) * 2022-03-11 2023-04-28 汕头市瑞升电子有限公司 一种高压低损陶瓷电容器介质及其制备方法
CN117153564A (zh) * 2023-09-06 2023-12-01 潮州三环（集团）股份有限公司 一种复合电子元件及其制备方法与应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0365558A (ja) * 1989-07-31 1991-03-20 Tdk Corp 誘電体磁器組成物
KR20010090884A (ko) * 1998-05-12 2001-10-19 무라타 야스타카 유전체 세라믹 조성물 및 적층 세라믹 커패시터
CN102101775A (zh) * 2010-12-08 2011-06-22 汕头高新区松田实业有限公司 一种低损耗高压陶瓷电容器介质
CN102399083A (zh) * 2010-09-14 2012-04-04 中国钢铁股份有限公司 介电陶瓷组合物
CN103351161A (zh) * 2013-03-11 2013-10-16 江苏大学 一种低温烧结高压陶瓷电容器介质
CN103693955A (zh) * 2013-07-05 2014-04-02 宝鸡宇鑫电子有限公司 一种陶瓷电容器瓷料及其制造方法

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5720270B2 (zh) * 1973-09-19 1982-04-27
US3959658A (en) * 1974-06-13 1976-05-25 Purdue Research Foundation Microwave dosimeter utilizing thermoluminescent materials
JP2870511B2 (ja) * 1996-12-03 1999-03-17 松下電器産業株式会社 誘電体磁器組成物とそれを用いた積層セラミックコンデンサとその製造方法
JP3417911B2 (ja) * 2000-08-21 2003-06-16 ティーディーケイ株式会社 誘電体磁器組成物の製造方法と誘電体層含有電子部品の製造方法
JP5153069B2 (ja) * 2005-10-26 2013-02-27 京セラ株式会社 誘電体磁器
JP2007258475A (ja) * 2006-03-23 2007-10-04 Tdk Corp 積層型電子部品およびその製造方法
TW200839814A (en) * 2007-03-14 2008-10-01 Tdk Corp Dielectric ceramic composition and electronic device
EP1980545B1 (en) * 2007-04-12 2009-12-09 TDK Corporation Dielectric ceramic composition and electronic device
JP4967963B2 (ja) * 2007-09-28 2012-07-04 Ｔｄｋ株式会社 誘電体磁器組成物および電子部品
WO2009070047A1 (en) * 2007-11-26 2009-06-04 Elizaveta Arkadievna Nenasheva Low dielectric loss ceramic ferroelectric composite material
JP5217405B2 (ja) * 2007-12-11 2013-06-19 Ｔｄｋ株式会社 誘電体磁器組成物および電子部品
JP5446880B2 (ja) * 2010-01-04 2014-03-19 Ｔｄｋ株式会社 誘電体磁器組成物および電子部品
JPWO2011125543A1 (ja) * 2010-04-02 2013-07-08 株式会社村田製作所 誘電体セラミックおよびそれを用いた積層セラミックコンデンサ
JP5224147B2 (ja) * 2010-09-28 2013-07-03 株式会社村田製作所 誘電体セラミック、及び積層セラミックコンデンサ
WO2012043208A1 (ja) * 2010-09-30 2012-04-05 株式会社村田製作所 誘電体セラミック、積層セラミック電子部品、およびこれらの製造方法
CN102176374B (zh) * 2011-03-10 2013-05-08 江苏大学 一种低温烧结的高压陶瓷电容器介质
JP5857570B2 (ja) * 2011-09-15 2016-02-10 株式会社村田製作所 積層セラミックコンデンサ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0365558A (ja) * 1989-07-31 1991-03-20 Tdk Corp 誘電体磁器組成物
KR20010090884A (ko) * 1998-05-12 2001-10-19 무라타 야스타카 유전체 세라믹 조성물 및 적층 세라믹 커패시터
CN102399083A (zh) * 2010-09-14 2012-04-04 中国钢铁股份有限公司 介电陶瓷组合物
CN102101775A (zh) * 2010-12-08 2011-06-22 汕头高新区松田实业有限公司 一种低损耗高压陶瓷电容器介质
CN103351161A (zh) * 2013-03-11 2013-10-16 江苏大学 一种低温烧结高压陶瓷电容器介质
CN103693955A (zh) * 2013-07-05 2014-04-02 宝鸡宇鑫电子有限公司 一种陶瓷电容器瓷料及其制造方法

Also Published As

Publication number Publication date
US9963393B2 (en) 2018-05-08
JP6334580B2 (ja) 2018-05-30
CN106348753A (zh) 2017-01-25
US20170015590A1 (en) 2017-01-19
TW201704187A (zh) 2017-02-01
JP2017024969A (ja) 2017-02-02
CN106348753B (zh) 2019-12-13

Similar Documents

Publication Publication Date Title
TWI573775B (zh) Ceramic capacitor dielectric material
JP4805938B2 (ja) 誘電体磁器およびその製法、並びに積層セラミックコンデンサ
JP5131595B2 (ja) 誘電体セラミック、及びセラミック電子部品、並びに積層セラミックコンデンサ
KR100444229B1 (ko) 내환원성 유전체 자기 조성물
JP5146475B2 (ja) 誘電体磁器組成物およびセラミック電子部品
KR102163417B1 (ko) 적층 세라믹 커패시터
JP5423682B2 (ja) 誘電体セラミックおよび積層セラミックコンデンサ
EP2266933A1 (en) Sintered material for dielectric substance and process for preparing the same
JP4522025B2 (ja) 誘電体磁器及び積層型電子部品並びに積層型電子部品の製法
KR20190121142A (ko) 적층 세라믹 커패시터
KR101732422B1 (ko) 유전체 제조용 소결 전구체 분말 및 이의 제조 방법
CN113880569A (zh) 一种多层片式陶瓷电容器的介质材料及其制备方法
KR101178952B1 (ko) 유전체 자기 조성물 및 전자 부품
CN112479705A (zh) 一种钛酸钡基x8r型多层陶瓷电容器用介质材料及制备方法
JPH11302072A (ja) 誘電体セラミック、積層セラミックコンデンサおよび積層セラミックコンデンサの製造方法
KR101659143B1 (ko) 유전체 자기 조성물 및 이를 포함하는 적층 세라믹 커패시터
KR20170081986A (ko) 유전체 조성물 및 이를 포함하는 적층 세라믹 커패시터
JP5541318B2 (ja) 誘電体磁器組成物およびセラミック電子部品
JP2020043310A (ja) 誘電体組成物および電子部品
TW202231601A (zh) 介電陶瓷組合物及使用其的陶瓷電容器
JP4463095B2 (ja) 積層セラミックコンデンサおよびその製法
KR100268702B1 (ko) 유전체세라믹조성물
JP2006179675A (ja) 積層セラミックコンデンサおよびその製法
KR100395089B1 (ko) Ｎｉ을 내부전극으로 하는 Ｙ5Ｖ 적층 칩캐퍼시터용 유전체 조성물
JP2007119274A (ja) 誘電体磁器