WO2015076005A1 - Procédé de frittage de céramiques et procédé de production d'un composant électronique céramique multicouche - Google Patents

Procédé de frittage de céramiques et procédé de production d'un composant électronique céramique multicouche Download PDF

Info

Publication number
WO2015076005A1
WO2015076005A1 PCT/JP2014/074469 JP2014074469W WO2015076005A1 WO 2015076005 A1 WO2015076005 A1 WO 2015076005A1 JP 2014074469 W JP2014074469 W JP 2014074469W WO 2015076005 A1 WO2015076005 A1 WO 2015076005A1
Authority
WO
WIPO (PCT)
Prior art keywords
ceramic
light
film
light absorption
conductive paste
Prior art date
Application number
PCT/JP2014/074469
Other languages
English (en)
Japanese (ja)
Inventor
清水　尚
Original Assignee
株式会社村田製作所
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 by 株式会社村田製作所 filed Critical 株式会社村田製作所
Priority to JP2015549021A priority Critical patent/JP6217760B2/ja
Publication of WO2015076005A1 publication Critical patent/WO2015076005A1/fr

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B17/00—Furnaces of a kind not covered by any preceding group
    • F27B17/0016—Chamber type furnaces
    • F27B17/0025—Especially adapted for treating semiconductor wafers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • 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
    • C04B2235/3231—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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6025—Tape casting, e.g. with a doctor blade
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/667—Sintering using wave energy, e.g. microwave sintering
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/34—Oxidic
    • C04B2237/345—Refractory metal oxides
    • C04B2237/346—Titania 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/68—Forming laminates or joining articles wherein at least one substrate contains at least two different parts of macro-size, e.g. one ceramic substrate layer containing an embedded conductor or electrode
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/70—Forming laminates or joined articles comprising layers of a specific, unusual thickness
    • C04B2237/704—Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the ceramic layers or articles
    • 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
    • H01G4/30—Stacked capacitors

Definitions

  • the present invention relates to a method for firing a ceramic and a method for producing a multilayer ceramic electronic component carried out using this firing method.
  • Patent Document 1 a method for manufacturing a multilayer ceramic electronic component is described in various documents such as International Publication No. 2004/075216 (Patent Document 1). According to the manufacturing method described in these prior art documents, the multilayer ceramic electronic component is manufactured through the following steps.
  • a conductive paste film having a pattern corresponding to a desired electrode pattern is printed on a ceramic green sheet formed on a film substrate, and then a plurality of ceramic green sheets are laminated to obtain a raw laminate.
  • the film substrate is peeled off before the ceramic green sheets are laminated, or is peeled off every time the ceramic green sheets are laminated while performing the lamination process.
  • the raw laminate is cut into an appropriate size as necessary, and then fired.
  • the resin component in the raw laminate is removed (degreasing), and the ceramic particles in the ceramic green sheet and the metal particles in the conductive paste film are sintered.
  • the external electrode is formed by baking a conductive paste.
  • a batch furnace or a tunnel furnace is applied.
  • the atmosphere in the furnace is heated to a temperature at which the ceramic is sintered (about 1300 ° C.) at a temperature rising rate of several to several tens of degrees per minute, and the electrode layer and the ceramic layer are sintered.
  • the metal particles start sintering earlier than the ceramic particles. Therefore, in the firing process, there is a stage where only the electrode layer shrinks and shrinks, and in such a stage where only the electrode layer shrinks, a relatively large stress is generated at the interface between the electrode layer and the ceramic layer.
  • defects such as delamination between layers (delamination defects) and defects in which the electrode layer contracts into a network and the electrode coverage decreases (coverage defects) occur.
  • the poor coverage causes a problem that desired electrical characteristics cannot be obtained in the obtained multilayer ceramic electronic component.
  • an object of the present invention is to provide a method for manufacturing a multilayer ceramic electronic component capable of suppressing the occurrence of the above-mentioned delamination failure and coverage failure.
  • Another object of the present invention is to provide a ceramic firing method that does not depend on atmosphere firing in a batch furnace or a tunnel furnace that may cause the above-mentioned problems of delamination and coverage. .
  • This invention is first directed to a ceramic firing method.
  • the present invention is characterized in that firing using a heating light source capable of instantaneous and rapid heating is applied instead of atmosphere firing such as a batch furnace or a tunnel furnace.
  • a heating light source capable of instantaneous and rapid heating
  • atmosphere firing such as a batch furnace or a tunnel furnace.
  • ceramic sheets such as dielectric ceramic sheets
  • a light absorption film having a light absorption rate higher than that of the ceramic sheet is formed on the ceramic sheet. In this state, the light absorption film is irradiated with light from the heating light source.
  • a step of preparing a ceramic sheet containing ceramic particles and a light absorption film having a light absorption rate higher than that of the ceramic sheet are formed on the ceramic sheet.
  • a light irradiation step of irradiating light from the heating light source toward the light absorption film is formed on the ceramic sheet.
  • the light absorption film is heated and heated by absorbing light.
  • the ceramic particles are sintered by heat transferred from the absorption film to the ceramic sheet.
  • the light absorption film is formed of a film that remains on the ceramic sheet even after the light irradiation step, as in the case of, for example, a conductive paste containing metal particles, As in the case of a paste containing a dark organic pigment, at least a part thereof may be a film that disappears in the light irradiation step.
  • the present invention is also directed to a method for manufacturing a multilayer ceramic electronic component that is carried out by applying the ceramic firing method described above.
  • a method for manufacturing a multilayer ceramic electronic component according to the present invention includes a step of preparing a plurality of ceramic sheets containing ceramic particles, a step of stacking a plurality of ceramic sheets, thereby obtaining a laminate, and a laminate A main firing step of firing.
  • the method of manufacturing a multilayer ceramic electronic component according to the present invention includes a step of forming a light absorption film having a light absorption rate higher than that of the ceramic sheet on the ceramic sheet, and heating.
  • the light irradiation process is a preliminary baking process performed prior to the above-described main baking process.
  • the particle size of the ceramic particles is preferably smaller than the particle size of the metal particles described above. This makes it possible to sinter ceramic particles faster than metal particles, and as a result, it is possible to realize a unique phenomenon that cannot occur in conventional atmosphere firing, in which the ceramic sheet shrinks before the conductive paste film. . This is considered to be effective in suppressing the occurrence of delamination failure and coverage failure.
  • a xenon lamp is preferably used as the heating light source.
  • the xenon lamp as described above, a large irradiation energy can be obtained. Therefore, the temperature of the light absorption film can be instantaneously increased, and accordingly, the ceramic sheet can be brought to a high temperature in a short time. Therefore, the sintering of the ceramic particles contained in the ceramic sheet and the sintering of the metal particles contained in the conductive paste film can be started almost simultaneously, and the occurrence of defective delamination and coverage can be more reliably suppressed.
  • the production yield of the multilayer ceramic electronic component can be improved.
  • the xenon lamp has a higher irradiation energy such that the irradiation energy is 0.5 kW / cm 2 or more.
  • the visible light absorption rate of the light absorption film is 21% or more. This is because the light absorption film is more efficiently heated by the light from the heating light source, and accordingly, the ceramic particles contained in the ceramic sheet can be sintered more rapidly.
  • a light irradiation process is implemented whenever it laminates
  • the ceramic sheets that have finished the light irradiation step are laminated.
  • the light irradiation step is performed every time the ceramic sheets on which the light absorption film is formed are stacked in the stacking step as in the former case.
  • the irradiation time per pulse of the xenon lamp is 10 milliseconds or less so that it is shorter.
  • the thickness of the ceramic sheet is preferably 0.1 to 10 ⁇ m. This is because the ceramic particles contained in the ceramic sheet are sufficiently sintered.
  • the ceramic particles are formed by the light from the heating light source by forming the light absorbing film. Can be sintered.
  • the firing by light can achieve the sintering of the ceramic particles more rapidly than the atmosphere firing using a batch furnace or a tunnel furnace.
  • the ceramic layer provided by the ceramic sheet and the conductivity The stress at the interface between the two due to the difference in contraction behavior between the electrode layer and the electrode layer provided by the paste film can be reduced, and therefore, the occurrence of delamination failure and coverage failure can be suppressed.
  • the conductive paste film also serves as at least a part of the light absorption film, and an electrode layer to be provided in the obtained multilayer ceramic electronic component is provided. It can be provided by at least part of the light absorbing film.
  • a multilayer ceramic capacitor 1 includes a multilayer body 5 including a plurality of laminated ceramic layers 2 and first and second internal electrode layers 3 and 4 disposed along a plurality of interfaces between the ceramic layers 2. It has.
  • the first internal electrode layer 3 and the second internal electrode layer 4 are opposed to each other in a part of each, and are alternately arranged as viewed in the stacking direction.
  • the ceramic layer 2 is made of, for example, a BaTiO 3 based dielectric ceramic, and the internal electrode layers 3 and 4 are mainly made of nickel, for example.
  • the laminate 5 includes first and second main surfaces 6 and 7 facing each other, first and second side surfaces facing each other (a surface parallel to a paper surface not shown), and first and second end surfaces facing each other. It has a substantially rectangular parallelepiped shape with 8 and 9.
  • Each end of the first internal electrode layer 3 is exposed at the first end face 8 of the multilayer body 5.
  • a first external electrode 10 is formed on the first end face 8 of the multilayer body 5 so as to be electrically connected to each end of the first internal electrode layer 3.
  • Each end of the second internal electrode layer 4 is exposed at the second end face 9 of the multilayer body 5.
  • a second external electrode 11 is formed on the second end face 9 of the multilayer body 5 so as to be electrically connected to each end of the second internal electrode layer 4.
  • External electrodes 10 and 11 are formed, for example, by applying a conductive paste containing copper or silver as a conductive component on end faces 8 and 9 of laminate 5 and heat-treating (baking) it.
  • plating films 12 and 13 are formed as necessary.
  • the plating films 12 and 13 include, for example, a nickel plating layer 14 mainly composed of nickel and a tin plating layer 15 mainly composed of tin formed thereon.
  • a raw ceramic sheet 21 (see FIG. 2) to be the ceramic layer 2 is prepared.
  • the ceramic sheet 21 is obtained by forming a ceramic slurry containing ceramic particles, a resin and a dispersant into a sheet shape on a film substrate.
  • a conductive paste for forming the internal electrode layers 3 and 4 is prepared.
  • the conductive paste includes, for example, metal particles made of nickel, a resin, and an organic solvent.
  • the conductive paste is printed with a predetermined pattern on the above-described ceramic sheet 21, thereby forming the conductive paste film 22 (see FIG. 2) to be the internal electrode layers 3 and 4 on the ceramic sheet 21. . If the metal particles contained in the conductive paste have a nano-level particle size, the conductive paste film 22 usually looks blackish. That is, the conductive paste film 22 has a light absorption rate higher than that of the whitish ceramic sheet 21. Therefore, in this embodiment, the conductive paste film 22 itself serves as a light absorption film.
  • a plurality of ceramic sheets 21 including the ceramic sheet 21 on which the conductive paste film 22 is formed are peeled off from a film base material (not shown), and then laminated to form a raw laminate. can get. This lamination process is shown in FIG.
  • a plurality of ceramic sheets 21 that are not formed with a conductive paste film and that are outer layer portions on one side in the stacking direction of the stacked body 5 are stacked.
  • a plurality of ceramic sheets 21 on which the conductive paste film 22 is formed are laminated.
  • a light irradiation process is performed in which the light 24 from the heating light source 23 is irradiated toward the conductive paste film 22 as a light absorption film.
  • the heating light source 23 a light source capable of irradiating a strong light 24 of preferably 0.5 kW / cm 2 or more, more preferably 1 kW / cm 2 or more is used.
  • a xenon lamp is advantageously used.
  • a halogen lamp other than a xenon lamp can be used as the heating light source 23.
  • a condensing optical system including a lens and a mirror may be combined.
  • the heating light source 23 When a xenon lamp is used as the heating light source 23, pulsed light 24 in the order of microseconds to milliseconds is irradiated. At this time, the dark conductive paste film 22 absorbs the light 24 and is heated, and at the same time, the heat is transmitted to the ceramic sheet 21 immediately below the conductive paste film 22.
  • the conductive paste film 22 is usually as thin as several ⁇ m, it can be considered that the conductive paste film 22 and the ceramic sheet 21 are heated almost simultaneously.
  • the energy of the irradiation light 24 is sufficiently large (for example, when it is 1 kW / cm 2 or more for each thickness of 1 ⁇ m of the conductive paste film 22 and the ceramic sheet 21; that is, when it is about 10,000 times or more of sunlight) ).
  • the conductive paste film 22 and the ceramic sheet 21 are instantaneously heated to 1000 ° C. or higher, and the metal contained in the conductive paste film 22 for a short time ( ⁇ several milliseconds) until the temperature starts to drop. Both the particles and the ceramic particles contained in the ceramic sheet 21 are sintered.
  • the conductive paste film 22 is heated by absorbing the light 24, and as a result, the metal particles contained in the conductive paste film 22 are sintered and the heated conductive paste is heated.
  • the ceramic particles contained in the ceramic sheet 21 are sintered by the heat transferred from the film 22 to the ceramic sheet 21.
  • particle sintering occurs from the point of contact necking between particles, and the speed is known to be inversely proportional to the particle size (written by Tsuneo Ishida, “Sintered Materials Engineering”, Morikita Publishing Co., Ltd.) , March 1997, pp. 77-82). Therefore, as described above, the sintering of the metal particles and the sintering of the ceramic particles start almost simultaneously. However, when the ceramic particles are smaller than the metal particles, more precisely, the ceramic particles are more than the metal particles. Sinters as soon as possible. Therefore, it is possible to realize a specific phenomenon that cannot occur in the conventional atmosphere firing, in which the ceramic sheet 21 contracts before the conductive paste film 22. This is considered to be effective in suppressing the occurrence of delamination failure and coverage failure.
  • Photo-firing is a short-time pre-firing process and is intended for necking of ceramic particles. Therefore, the sintering of the metal particles and the full-scale sintering (densification) of the ceramic particles are performed using a conventional atmospheric furnace in the main firing step described later. At this time, since the ceramic particles are preliminarily contracted, the stress at the interface between the conductive paste film 22 and the ceramic sheet 21 in the process of sintering the metal particles and the ceramic particles in this order can be reduced. As a result, it is possible to reduce defects such as delamination and electrode coverage and improve yield.
  • the laminated body 5 A plurality of ceramic sheets 21 on which the conductive paste film is not formed, which is the outer layer portion on the other side in the laminating direction, are laminated.
  • the laminated body obtained as described above is pressed in the laminating direction.
  • a preliminary press may be further performed for each stacking of the ceramic sheets 21 at a stage in the middle of the above-described lamination process.
  • the conductive paste film 22 that absorbs more light serves as a main heat source and the ceramic sheet 21 is heated. Therefore, the ceramic particles are sintered immediately below the conductive paste film 22. There is a high possibility that the ceramic particles are not sintered in the periphery of the ceramic sheet 21, for example, in the peripheral portion. Therefore, there is a high possibility that the resin component as the binder remains in the peripheral portion of the ceramic sheet 21. However, this resin component advantageously acts to further improve the adhesion between the ceramic sheets 21 in the laminated body after pressing.
  • a cutting step is performed as necessary in order to obtain a laminated body before the main firing for the individual multilayer ceramic capacitors 1 shown in FIG. And the main baking process by atmospheric baking using a batch furnace, a tunnel furnace, etc. is implemented, and the laminated body 5 sintered is obtained.
  • a conductive paste is applied on the end faces 8 and 9 of the laminate 5 and baked, whereby external electrodes 10 and 11 are formed. Furthermore, plating films 12 and 13 are formed on the external electrodes 10 and 11 as necessary, and the multilayer ceramic capacitor 1 is completed.
  • the manufacturing method according to the present invention is not limited to the multilayer ceramic capacitor as described above, and can be applied to other multilayer ceramic electronic components such as a positive temperature coefficient thermistor, varistor, and inductor. .
  • FIG. 3 is a view for explaining a manufacturing method according to the second embodiment of the present invention. 3, elements corresponding to those shown in FIG. 2 are denoted by the same reference numerals, and redundant description is omitted.
  • This embodiment is characterized in that the ceramic sheets that have undergone the light irradiation step are laminated in the lamination step.
  • FIG. 3 shows a long ceramic sheet 21 lined with a film substrate 25. While the ceramic sheet 21 is intermittently conveyed in the direction of the arrow 26 by a roll-to-roll method (not shown), the conductive paste film 22 is printed at the printing station 27, and then the heater heating and drying station 28 is moved. After that, in the light irradiation station 29, the light 24 from the heating light source 23 is irradiated toward the conductive paste film 22. In this light irradiation station 29, the conductive paste film 22 is heated by absorbing the light 24, the metal particles are sintered, and the heat transferred from the heated conductive paste film 22 to the ceramic sheet 21 The ceramic particles sinter.
  • the ceramic sheet 21 is cut along the cutting line 30 and then subjected to a lamination process (not shown).
  • a lamination process not shown.
  • the same steps as those described with reference to FIG. 2 are performed except that the light irradiation step is not performed.
  • FIG. 4 is a view for explaining a manufacturing method according to the third embodiment of the present invention. 4, elements corresponding to those shown in FIG. 2 are denoted by the same reference numerals, and redundant description is omitted.
  • This embodiment is characterized in that not only the conductive paste film remaining on the ceramic sheet after the light irradiation process but also a film that disappears in the light irradiation process is provided as the light absorption film.
  • a conductive paste film 22 is formed on the ceramic sheet 21 with a predetermined pattern. Further, in the region where the conductive paste film 22 is not formed on the ceramic sheet 21, a erasable film 31 made of a paste containing carbon or a dark organic pigment is formed, for example, which disappears in the light irradiation process. Note that the order of forming the conductive paste film 22 and the erasable film 31 is not limited.
  • the conductive paste film 22 and the erasable film 31 are lighted. 24 is absorbed and heated, and at the same time, the heat is transmitted to the ceramic sheet 21 immediately below the conductive paste film 22 and the erasable film 31.
  • the metal particles in the conductive paste film 22 are sintered and the ceramic particles in the ceramic sheet 21 are sintered.
  • the erasable film 31 disappears by heat generated by absorbing the light 24 itself. The disappearance of the lossable film 31 is accompanied by phenomena such as evaporation and combustion.
  • sintering of the ceramic particles can be achieved over the entire region in the main surface direction of the ceramic sheet 21.
  • FIG. 5 illustrates a manufacturing method according to the fourth embodiment of the present invention.
  • elements corresponding to those shown in FIG. 2 or 4 are denoted by the same reference numerals, and redundant description is omitted.
  • this embodiment includes not only a conductive paste film remaining on the ceramic sheet after the light irradiation process but also a film that disappears in the light irradiation process as the light absorption film. It is characterized by that. Further, this embodiment is the same as the third embodiment in that the sintering of the ceramic particles can be achieved over the entire region in the main surface direction of the ceramic sheet.
  • a conductive paste film 22 is formed on the ceramic sheet 21 with a predetermined pattern. Further, the erasable film 31 that disappears in the light irradiation process is formed in the entire region in the main surface direction of the ceramic sheet 21 including the region where the conductive paste film 22 is formed on the ceramic sheet 21.
  • the conductive paste film 22 and the erasable film 31 as the light absorption film are heated by the light 24 from the heating light source 23, and at the same time, the heat is transferred to the conductive paste film 22 and the erasable film. It is transmitted to the ceramic sheet 21 immediately below 31. As a result, the metal particles in the conductive paste film 22 are sintered and the ceramic particles in the ceramic sheet 21 are sintered. Further, the erasable film 31 disappears by heat generated by absorbing the light 24 itself.
  • FIG. 6 illustrates a manufacturing method according to the fifth embodiment of the present invention.
  • elements corresponding to the elements shown in FIG. 4 are denoted by the same reference numerals, and redundant description is omitted.
  • This embodiment is characterized in that only a film that disappears in the light irradiation step is provided as the light absorption film. Also in this embodiment, the sintering of the ceramic particles can be achieved over the entire region in the main surface direction of the ceramic sheet.
  • a erasable film 31 that disappears in the light irradiation process is formed in the entire region in the main surface direction of the ceramic sheet 21.
  • the lossable film 31 for example, application by printing or spraying is applied.
  • the light 24 from the heating light source 23 heats the erasable film 31 as a light absorption film, and at the same time, the heat is transmitted to the ceramic sheet 21 immediately below the erasable film 31.
  • the ceramic particles in the ceramic sheet 21 are sintered, and the erasable film 31 disappears by heat generated by absorbing the light 24 itself.
  • BaCO 3 and TiO 2 powders were prepared and prepared so that the composition of BaTiO 3 was obtained.
  • a resin, a dispersant, and water were added to the calcined powder and mixed with zirconia balls for several hours to obtain a ceramic slurry containing the calcined powder as ceramic particles having an average particle diameter of 50 nm.
  • the ceramic slurry was formed into a sheet shape by a doctor blade method on a film substrate and dried to obtain a ceramic sheet having a thickness of 2 ⁇ m.
  • a conductive paste containing nickel powder having an average particle diameter of 200 nm, a resin, and an organic solvent is prepared, and a conductive paste having a thickness of 1.0 ⁇ m serving as an internal electrode layer is formed on a predetermined ceramic sheet by a screen printing method. A film was formed.
  • the particle size of the ceramic particles described above is smaller than the particle size of the nickel powder as the metal powder.
  • the conductive paste film is placed on the ceramic sheet so that the conductive paste film faces the ceramic sheet.
  • a plurality of ceramic sheets formed with the above were laminated.
  • each time one ceramic sheet is stacked light (wavelength 300 to 1200 nm) from a mercury xenon lamp is directed toward the conductive paste film as “irradiation light power” and “irradiation” shown in Table 1.
  • the laser sheet was pre-fired by irradiating 1 pulse with time.
  • an appropriate number of outer layer ceramic sheets on which a conductive paste film is not formed are laminated and pressure-bonded, and then cut into dimensions of 2.2 mm in length and 2.75 mm in width, and 1.2 mm in thickness. A raw laminate was obtained.
  • the raw laminate was degreased at a temperature of 400 ° C. and then baked at a temperature of 1250 ° C. for 20 minutes for main baking.
  • a sintered laminate was obtained in which the ceramic layer was provided by the ceramic sheet and the internal electrode layer was provided by the conductive paste film.
  • the sintered laminate was mixed with a cobblestone having a diameter of 1 mm containing Si and Al, and a predetermined amount of water was added to perform barrel polishing.
  • an external electrode is formed by applying and baking a conductive paste containing Cu as a conductive component on both end faces of the laminate, and then, on the external electrode, an Ni layer and Sn as a plating film are further formed. Layers were sequentially formed by electroplating.
  • the delamination occurrence rate was reduced while maintaining the room temperature resistance as compared with the comparative sample. This is because the ceramic particles were sufficiently sintered by pre-firing with a mercury xenon lamp, and the stress caused by the difference in sintering shrinkage behavior between the internal electrode layer and the ceramic layer in the main firing stage was alleviated. Guessed.
  • the appropriate range of “irradiation light power” is considered to vary depending on the composition, particle size, film thickness, and the like of the ceramic material. However, in this experimental example, it was demonstrated that the ceramic particles can be sufficiently sintered by pre-firing with a mercury xenon lamp at least if the “irradiation light power” is 0.5 kW / cm 2 or more.
  • the light irradiation time per ceramic sheet of the layer is preferably shorter.
  • the “irradiation time” was in the range of 0.5 to 10 milliseconds.
  • the time required for laminating one ceramic sheet is about several hundred milliseconds to several seconds.
  • the “irradiation time” at which the above-mentioned good results were obtained is sufficiently short. Therefore, it is possible to introduce a preliminary baking step using light without reducing the efficiency of the conventional lamination step.
  • FIG. 7 shows an absorption spectrum of visible light (wavelength: 400 nm to 800 nm) for the light absorption film investigated in this experimental example.
  • the light absorption rate was measured using an ultraviolet-visible spectrophotometer (Shimadzu Corporation).
  • nickel is a light absorbing film formed by printing and applying a conductive paste containing nickel powder used in Experimental Example 1 onto the ceramic sheet used in Experimental Example 1.
  • Copper uses a copper powder having an average particle size of 200 nm, and a conductive paste produced by the same manufacturing method as that of the conductive paste containing the nickel powder is printed on the ceramic sheet used in Experimental Example 1. It is the formed light absorption film.
  • Silver foil is a light absorbing film formed on the ceramic sheet used in Experimental Example 1 by sputtering so that the silver foil has a thickness of 200 nm.
  • “None (ceramic)” is the ceramic sheet itself used in Experimental Example 1 in which no light absorption film was formed.
  • Table 2 shows whether or not each sample shown in FIG. 7 is irradiated with light and the ceramic particles contained in the ceramic sheet can be sintered.
  • “nickel” had an average light absorption rate of 63%
  • “copper” had an average light absorption rate of 21%.
  • the ceramic particles were sintered.
  • “silver foil” had an average light absorptivity of 0.7%, which was lower than “none (ceramic)”.
  • the ceramic particles were not sintered. Of course, the ceramic particles were not sintered even in “None (ceramic)”.
  • the average absorption rate of visible light is preferably 21% or more, more preferably 63% or more. I found out.
  • a non-volatile and non-combustible material called a metal material was used in the light absorption film.
  • a volatile material represented by an organic dye or a combustible material represented by carbon was used. It is understood that the same effect can be obtained even when used in a light absorbing film.
  • the thickness of the ceramic sheet as the object of photo-fired is preferably 0.1 to 10 ⁇ m, more preferably 0.1 to 3 ⁇ m.
  • Multilayer ceramic capacitors multilayer ceramic electronic components
  • Ceramic layer 3 Internal electrode layer 5
  • Laminate 21 Ceramic sheet 22
  • Conductive paste film 23 Heating light source 24
  • Light 29 Light irradiation station 30
  • Cutting line 31 Erasable film

Abstract

La présente invention concerne un procédé de production d'un composant électronique céramique multicouche qui peut supprimer les survenues de défauts de délamination dans un corps stratifié et de défauts de couverture d'une couche d'électrode interne. Chaque fois qu'une feuille de céramique (21) sur laquelle est formé un film adhésif conducteur (22) présentant un taux d'absorption de la lumière relativement élevé est stratifiée, la lumière (24) issue d'une source lumineuse chauffante (23) comme une lampe au xénon est appliquée sur le film adhésif conducteur (22). Le film adhésif conducteur (22) est chauffé par absorption de la lumière (24) ; il en résulte que des particules métalliques dans le film adhésif conducteur (22) sont frittées et les particules de céramique dans la feuille de céramique (21) sont frittées par la chaleur transmise depuis le film adhésif conducteur (22) vers la feuille de céramique (21). Un corps stratifié obtenu par stratification d'une pluralité des feuilles de céramique (21) est ensuite fritté après cela.
PCT/JP2014/074469 2013-11-20 2014-09-17 Procédé de frittage de céramiques et procédé de production d'un composant électronique céramique multicouche WO2015076005A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015549021A JP6217760B2 (ja) 2013-11-20 2014-09-17 セラミックの焼成方法および積層セラミック電子部品の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013239431 2013-11-20
JP2013-239431 2013-11-20

Publications (1)

Publication Number Publication Date
WO2015076005A1 true WO2015076005A1 (fr) 2015-05-28

Family

ID=53179277

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/074469 WO2015076005A1 (fr) 2013-11-20 2014-09-17 Procédé de frittage de céramiques et procédé de production d'un composant électronique céramique multicouche

Country Status (2)

Country Link
JP (1) JP6217760B2 (fr)
WO (1) WO2015076005A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020102634A1 (fr) * 2018-11-17 2020-05-22 Utility Global, Inc. Procédé de fabrication de réacteurs électrochimiques
US20200303749A1 (en) * 2018-11-12 2020-09-24 Utility Global, Inc. Copper Electrode and Method of Making
EP3877152A4 (fr) * 2018-11-06 2022-10-12 Utility Global, Inc. Système et procédé de dépôt et de chauffage intégrés
US11603324B2 (en) 2018-11-06 2023-03-14 Utility Global, Inc. Channeled electrodes and method of making
US11611097B2 (en) 2018-11-06 2023-03-21 Utility Global, Inc. Method of making an electrochemical reactor via sintering inorganic dry particles
US11761100B2 (en) 2018-11-06 2023-09-19 Utility Global, Inc. Electrochemical device and method of making

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61181008A (ja) * 1985-02-07 1986-08-13 住友金属鉱山株式会社 誘電体磁器の製造方法
JPS63230802A (ja) * 1987-03-20 1988-09-27 Hitachi Ltd 電子部品及びその製造方法
JPH09124382A (ja) * 1995-10-30 1997-05-13 Kyocera Corp セラミック基板の製造方法
CN103108499A (zh) * 2013-01-17 2013-05-15 中国科学院苏州纳米技术与纳米仿生研究所 柔性电子电路的封装方法及封装装置

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011012867A (ja) * 2009-07-01 2011-01-20 Murata Mfg Co Ltd 太陽エネルギー吸収体ならびにその製造方法および製造装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61181008A (ja) * 1985-02-07 1986-08-13 住友金属鉱山株式会社 誘電体磁器の製造方法
JPS63230802A (ja) * 1987-03-20 1988-09-27 Hitachi Ltd 電子部品及びその製造方法
JPH09124382A (ja) * 1995-10-30 1997-05-13 Kyocera Corp セラミック基板の製造方法
CN103108499A (zh) * 2013-01-17 2013-05-15 中国科学院苏州纳米技术与纳米仿生研究所 柔性电子电路的封装方法及封装装置

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3877152A4 (fr) * 2018-11-06 2022-10-12 Utility Global, Inc. Système et procédé de dépôt et de chauffage intégrés
EP3877180A4 (fr) * 2018-11-06 2022-12-14 Utility Global, Inc. Procédé et système de fabrication d'une pile à combustible
US11557784B2 (en) 2018-11-06 2023-01-17 Utility Global, Inc. Method of making a fuel cell and treating a component thereof
US11575142B2 (en) 2018-11-06 2023-02-07 Utility Global, Inc. Method and system for making a fuel cell
US11603324B2 (en) 2018-11-06 2023-03-14 Utility Global, Inc. Channeled electrodes and method of making
US11611097B2 (en) 2018-11-06 2023-03-21 Utility Global, Inc. Method of making an electrochemical reactor via sintering inorganic dry particles
US11735755B2 (en) 2018-11-06 2023-08-22 Utility Global, Inc. System and method for integrated deposition and heating
US11761100B2 (en) 2018-11-06 2023-09-19 Utility Global, Inc. Electrochemical device and method of making
US20200303749A1 (en) * 2018-11-12 2020-09-24 Utility Global, Inc. Copper Electrode and Method of Making
US11539053B2 (en) 2018-11-12 2022-12-27 Utility Global, Inc. Method of making copper electrode
WO2020102634A1 (fr) * 2018-11-17 2020-05-22 Utility Global, Inc. Procédé de fabrication de réacteurs électrochimiques

Also Published As

Publication number Publication date
JPWO2015076005A1 (ja) 2017-03-16
JP6217760B2 (ja) 2017-10-25

Similar Documents

Publication Publication Date Title
JP6217760B2 (ja) セラミックの焼成方法および積層セラミック電子部品の製造方法
US8332996B2 (en) Conductive paste composition for inner electrodes and method of manufacturing multilayer capacitor
JP2012227260A (ja) 積層セラミックコンデンサ
TW201302660A (zh) 塗佈金屬箔的陶瓷之製造方法以及金屬箔陶瓷電容器之形成方法
KR20110065623A (ko) 적층 세라믹 커패시터
KR20110067509A (ko) 외부전극용 도전성 페이스트 조성물, 이를 포함하는 적층 세라믹 커패시터 및 그 제조방법
JP3785966B2 (ja) 積層セラミック電子部品の製造方法および積層セラミック電子部品
KR101964368B1 (ko) 적층 세라믹 콘덴서 및 그 제조 방법
KR20190118957A (ko) 적층 세라믹 콘덴서 및 그 제조 방법
JP5083409B2 (ja) 積層セラミック電子部品の製造方法
WO2005036571A1 (fr) Pate a electrodes, composant electronique en ceramique, procede de production correspondant
JPH09106925A (ja) 積層セラミックコンデンサの製造方法
JP2004096010A (ja) 積層型セラミック電子部品の製造方法
JP5251589B2 (ja) セラミックコンデンサの製造方法
JP2004289090A (ja) 積層セラミック電子部品の製造方法
JP2005286014A (ja) 導電ペースト
JP4702972B2 (ja) 積層型電子部品およびその製法
JP2005303029A (ja) 積層セラミック電子部品の製造方法
KR101376912B1 (ko) 내부전극용 도전성 페이스트 조성물 및 이를 이용한 적층 세라믹 전자부품
JP2005109218A (ja) 電極ペースト及びこれを用いたセラミック電子部品の製造方法
JP2018056433A (ja) 積層セラミック電子部品の内部電極膜の評価方法、並びに、積層セラミック電子部品の製造方法
JP2005142352A (ja) 内部電極用シートおよびその製造方法
JP2005101318A (ja) 導電性ペースト及びそれを用いたセラミック電子部品の製造方法
JP2005251612A (ja) 導電性ペースト用Ｎｉ粉末、導電性ペースト、およびそれを用いたセラミック電子部品
JP4808534B2 (ja) 導電性ペースト及びセラミック電子部品の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14864400

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015549021

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14864400

Country of ref document: EP

Kind code of ref document: A1