WO2016125520A1 - Élément semi-conducteur et son procédé de fabrication - Google Patents

Élément semi-conducteur et son procédé de fabrication Download PDF

Info

Publication number
WO2016125520A1
WO2016125520A1 PCT/JP2016/050205 JP2016050205W WO2016125520A1 WO 2016125520 A1 WO2016125520 A1 WO 2016125520A1 JP 2016050205 W JP2016050205 W JP 2016050205W WO 2016125520 A1 WO2016125520 A1 WO 2016125520A1
Authority
WO
WIPO (PCT)
Prior art keywords
ceramic
semiconductor element
particles
internal electrode
ceramic body
Prior art date
Application number
PCT/JP2016/050205
Other languages
English (en)
Japanese (ja)
Inventor
浩平 深町
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 DE112016000618.7T priority Critical patent/DE112016000618T5/de
Priority to JP2016573240A priority patent/JP6739353B2/ja
Priority to CN201680007338.7A priority patent/CN107210105B/zh
Publication of WO2016125520A1 publication Critical patent/WO2016125520A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/006—Alkaline earth titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H01C7/022—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
    • H01C7/023—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances containing oxides or oxidic compounds, e.g. ferrites
    • H01C7/025—Perovskites, e.g. titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/18—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material comprising a plurality of layers stacked between terminals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • 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
    • C04B2235/50—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
    • C04B2235/5409—Particle size related information expressed by specific surface values
    • 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
    • C04B2235/652—Reduction treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6582—Hydrogen containing atmosphere
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • C04B2235/662—Annealing after sintering
    • C04B2235/663—Oxidative annealing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/761—Unit-cell parameters, e.g. lattice constants
    • 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
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/785—Submicron sized grains, i.e. from 0,1 to 1 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/79—Non-stoichiometric products, e.g. perovskites (ABO3) with an A/B-ratio other than 1

Definitions

  • the present invention relates to a semiconductor element and a manufacturing method thereof, and more particularly to a barium titanate-based semiconductor element and a manufacturing method thereof.
  • barium titanate-based semiconductor ceramics have a positive temperature characteristic, they are widely used in semiconductor elements such as a positive temperature coefficient thermistor (PTC thermistor).
  • PTC thermistor positive temperature coefficient thermistor
  • Patent Document 1 discloses a temperature characterized by discontinuously dispersing and adhering child particles made of metal particles that are in ohmic contact with the mother particles to the surface of the mother particles made of semiconductor particles having nonlinear temperature characteristics. A method for producing characteristic-functional composite particles is described. The composite particles described in Patent Document 1 are not subjected to high-temperature sintering, and the composite particles are dispersed in a solvent and applied, or as a green compact. It can be used as such.
  • Patent Document 2 discloses an insulating ceramic substrate, a thermistor thick film having a positive resistance temperature characteristic formed of a semiconductor ceramic sintered body formed on the insulating ceramic substrate, a thermistor thick film in contact with the thermistor thick film.
  • a positive temperature coefficient thermistor is described, comprising at least one pair of electrodes facing each other across at least a part of the film, wherein the thermistor thick film has a resistivity at room temperature of less than 10 k ⁇ ⁇ cm. .
  • the positive temperature coefficient thermistor described in Patent Document 2 can widen the contact area between crystal grains in the semiconductor ceramic constituting the thermistor thick film, and can reduce the resistance.
  • Patent Document 3 discloses a barium titanate-based semiconductor ceramic having an average ceramic particle size of 0.9 ⁇ m or less. Patent Document 3 describes that barium titanate semiconductor ceramics having an average ceramic particle size in the above range have a small specific resistance at room temperature and an excellent withstand voltage strength. Patent Document 3 discloses that the above-mentioned barium titanate-based semiconductor ceramic has a particle size of 0.1 ⁇ m or less, a crystal structure of cubic, a lattice constant of 4.020 angstroms or more, and a small amount of semiconductor. It is described that a barium titanate powder in which an agent is solid-solved or a product obtained by calcining the barium titanate powder is used as a raw material powder and is fired.
  • PTC thermistors are used in a wide variety of electronic devices to protect against overcurrent. With the recent increase in functionality of electronic devices, a PTC thermistor capable of handling particularly a large current has been demanded, and a PTC thermistor element having high withstand voltage characteristics has been developed. In order to improve the withstand voltage characteristics of the PTC thermistor, semiconductor ceramics constituting the PTC thermistor are made fine (Patent Document 3). However, as a result of repeated studies by the present inventor, it has been clarified that there is a problem that the specific resistance at room temperature of the PTC thermistor increases due to the formation of fine particles.
  • Patent Document 2 describes that the resistance is reduced by increasing the contact area between crystal grains in the semiconductor ceramic.
  • the crystal particles described in Patent Document 2 have a large particle size with an average particle size of 2 to 38 ⁇ m.
  • An object of the present invention is to provide a semiconductor device having a high withstand voltage characteristic and a low specific resistance at room temperature, and a method for manufacturing the same.
  • the present inventor conducted research while paying attention to the physical properties of perovskite type compound particles which are starting materials for manufacturing a semiconductor element.
  • the specific surface area of the perovskite-type compound particles and the ratio of the c-axis length to the a-axis length (tetragonal) c / a of the crystal lattice of the perovskite-type compound particles ceramics constituting the semiconductor element.
  • the inventors have found that it is possible to achieve both the fine particle formation of the ceramic sintered body particles contained in the element body and the improvement of the contact ratio of the ceramic sintered body particles, and have completed the present invention.
  • a ceramic body including ceramic sintered body particles; A first external electrode disposed on a first end face of the ceramic body, A semiconductor element including a second external electrode disposed on a second end face of the ceramic body, Ceramic sintered body particles are perovskite type compounds containing at least Ba and Ti, The average particle size of the ceramic sintered body particles is 0.4 ⁇ m or more and 1.0 ⁇ m or less, The total perimeter L G of ceramic sintered body particles present in one region, calculated by observing one region selected in one cross section of the semiconductor element with a scanning electron microscope, Total L NC of the perimeter of pores (pores) existing in the region, outer peripheral length L S of one region, and the following formula In represented, based on the value of the contact length L C of the ceramic sintered particles present in one area, the following formula A semiconductor element in which the contact ratio of the ceramic sintered body particles calculated by the above is 45% or more is provided.
  • the contact ratio of the ceramic sintered body particles is preferably 45% or more and 80% or less.
  • the semiconductor element described above may be a stacked semiconductor element in which one or more first internal electrodes and one or more second internal electrodes are arranged inside a ceramic body.
  • the first internal electrode is electrically connected to the first external electrode at the first end face of the ceramic body
  • the second internal electrode is connected to the second end face of the ceramic base body at the second end face. Electrically connected to the external electrode.
  • the first internal electrode and the second internal electrode may be Ni electrodes.
  • a method for manufacturing a semiconductor element Preparing perovskite-type compound particles containing at least Ba and Ti; Forming a green chip containing perovskite-type compound particles; Obtaining a ceramic body by firing a green chip; Forming a semiconductor element by forming external electrodes on both end faces of the ceramic body,
  • the specific surface area of the perovskite type compound particles is 4.0 m 2 / g or more and 14.0 m 2 / g or less,
  • a method is provided wherein the ratio c / a of the c-axis length to the a-axis length of the crystal lattice of the perovskite type compound particles is 1.005 or more and 1.009 or less.
  • the specific surface area of the perovskite type compound particles is preferably 4.0 m 2 / g or more and 11.0 m 2 / g or less.
  • the step of forming the green chip containing the perovskite type compound particles Producing a ceramic green sheet containing perovskite type compound particles; Applying a conductive paste for internal electrodes on the main surface of the ceramic green sheet; A step of obtaining a laminate by laminating a plurality of the ceramic green sheets coated with the internal electrode conductive paste; And placing a ceramic green sheet not coated with the internal electrode conductive paste on the upper and lower sides of the laminate and pressing the ceramic green sheet, and cutting to a predetermined size to obtain a green chip.
  • the above-mentioned internal electrode conductive paste may contain Ni metal powder as the conductive powder.
  • the semiconductor element according to the present invention has a high withstand voltage characteristic and a low specific resistance at room temperature due to the above configuration. Moreover, the manufacturing method of the semiconductor element which concerns on this invention can manufacture the semiconductor element which has a high withstand voltage characteristic and has a low specific resistance at room temperature by having the said structure.
  • FIG. 1 is a schematic cross-sectional view of a semiconductor device according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of a modification of the semiconductor device according to one embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view of another modification of the semiconductor device according to one embodiment of the present invention.
  • 4, in one section of the ceramic body is a diagram showing a total L G around the length of the ceramic sintered particles present in the SEM observation region.
  • 5 in one section of the ceramic body is a diagram showing a total L NC of perimeter of the pores existing in SEM observation region.
  • FIG. 6 is a diagram showing the outer peripheral length L S of the SEM observation region in one cross section of the ceramic body.
  • FIG. 1 is a schematic cross-sectional view of a semiconductor element 1 according to this embodiment.
  • the semiconductor element 1 according to this embodiment is a PTC thermistor.
  • a semiconductor element 1 shown in FIG. 1 is disposed on a ceramic body 2, a first external electrode 31 disposed on a first end surface 21 of the ceramic body 2, and a second end surface 22 of the ceramic body 2.
  • Second external electrode 32 is disposed on a ceramic body 2, a first external electrode 31 disposed on a first end surface 21 of the ceramic body 2, and a second end surface 22 of the ceramic body 2.
  • the ceramic body 2 includes ceramic sintered body particles.
  • the sintered ceramic particles are made of a ceramic material in which a donor element is added to barium titanate.
  • the ceramic sintered body particles are a perovskite type compound containing at least Ba and Ti.
  • the perovskite-type compound includes, in addition to Ba and Ti, at least one element selected from the group consisting of rare earth elements excluding Pm, Tm, Yb and Lu and / or a group consisting of Nb, W, Sb and Ta. It may contain at least one element selected.
  • At least one element selected from the group consisting of rare earth elements excluding Pm, Tm, Yb and Lu is at least one element selected from the group consisting of “element ⁇ ”, Nb, W, Sb and Ta Is also referred to as “element ⁇ ”.
  • the elements ⁇ and ⁇ are donors (semiconductor agents) for imparting PTC characteristics to the ceramic body 2.
  • the ceramic sintered body particles may include only one of the above-described element ⁇ and element ⁇ , or may include both elements ⁇ and ⁇ .
  • the ceramic body 2 preferably contains 99.5 mol parts or more and 100.5 mol parts or less of Ba when the total mol portion of Ti and ⁇ is 100 mol parts.
  • the ceramic body 2 may contain the above-described element ⁇ and / or element ⁇ in addition to Ba and Ti.
  • the ceramic body 2 contains the element ⁇ and / or the element ⁇ in such an amount that the total content of the elements ⁇ and ⁇ in the ceramic body 2 is 0.020 mol part or more and 0.500 mol part or less. Is preferred.
  • the ceramic body 2 may further contain Si derived from a sintering aid described later.
  • the ceramic body 2 may contain 3 mol parts or less of Si with respect to 100 mol parts of Ti.
  • the ceramic body 2 may further contain Zr that can inevitably be mixed in the manufacturing process. Zr may occur due to the use of zirconia balls as a grinding and dispersion medium when preparing a ceramic slurry described later.
  • the ceramic body 2 may contain 0.01 mol part or more and 1 mol part or less of Zr with respect to 100 mol parts of Ti.
  • the average particle diameter of the ceramic sintered body particles contained in the ceramic body 2 is 0.4 ⁇ m or more and 1.0 ⁇ m or less. When the average particle size is 0.4 ⁇ m or more, a low specific resistance can be achieved. When the average particle size is 1.0 ⁇ m or less, the semiconductor device 1 can achieve high withstand voltage characteristics.
  • the average particle diameter of the sintered ceramic particles can be calculated by observing a cross section of the semiconductor element with a scanning electron microscope (SEM) and performing image analysis.
  • the room temperature is low.
  • the specific resistance at (25 ° C.) can be lowered.
  • the contact rate of the ceramic sintered body particles is used as an index for evaluating the contact area between the ceramic sintered body particles.
  • the contact ratio of the ceramic sintered body particles can be calculated by the procedure described below. First, the semiconductor element 1 is polished to expose a cross section, and the cross section is observed with a scanning electron microscope (SEM). The cross section to be observed with the SEM is not particularly limited, and an arbitrary cross section may be selected.
  • the cross section is obtained by, for example, polishing the semiconductor element 1 in the LT plane (plane perpendicular to the W direction) to about 1/2 W point (about half the W dimension of the semiconductor element).
  • the cross section of the semiconductor element may be parallel to.
  • the region to be observed with the SEM is not particularly limited, but may be, for example, a region sandwiched between internal electrodes in the vicinity of the central portion of the ceramic body 2.
  • the size and magnification of the observation region can be set as appropriate so that the number of ceramic sintered particles in the measurement region can be counted from about 70 to about 200.
  • the outer perimeter length L S is obtained. Examples of the results of obtaining L G , L NC and L S by image analysis are shown in FIGS.
  • Total L NC around the length of the pores shown in Figure 5 the length of the portion not in contact with the adjacent ceramic sintered particles of perimeter of the ceramic sintered particles (hereinafter, "non-contact length It can be regarded as the sum of “
  • the outer peripheral length L S of the observation region is in contact with the ceramic sintered particles present in the observation region among the peripheral lengths of the ceramic sintered particles located at the outermost edge of the observation region.
  • the contact length of the ceramic sintered body particles is obtained.
  • the contact ratio of the ceramic sintered body particles can be calculated using the following formula. The higher the contact ratio of the ceramic sintered body particles, the larger the contact area between the ceramic sintered body particles. In the semiconductor element 1 according to this embodiment, the contact ratio of the ceramic sintered body particles is 45% or more.
  • the contact ratio is 45% or more, the specific resistance at room temperature (25 ° C.) can be lowered even when the average particle diameter of the ceramic sintered body particles is small.
  • the contact ratio of the ceramic sintered body particles is preferably 45% or more and 80% or less. When the contact ratio is 80% or less, high PTC (positive temperature coefficient) characteristics can be achieved.
  • the dimensions of the ceramic body 2 are not particularly limited, and can be set as appropriate according to the application.
  • the dimension of the ceramic body 2 may be, for example, L dimension 2.0 mm ⁇ W dimension 1.2 mm ⁇ T dimension 1.0 mm.
  • the direction from the first end face 21 to the second end face 22 of the ceramic body 2 is the “L direction”, and the direction perpendicular to the L direction in the horizontal plane. Is called the “W direction”, and the direction perpendicular to the L direction and the W direction is called the “T direction”.
  • the dimension of the ceramic body 2 in the L direction is referred to as “L dimension”, the dimension in the W direction as “W dimension”, and the dimension in the T direction as “T dimension”.
  • the semiconductor element 1 is a stacked semiconductor in which one or more first internal electrodes 41 and one or more second internal electrodes 42 are arranged inside a ceramic body 2. It may be an element.
  • the first internal electrode 41 and the second internal electrode 42 may be collectively referred to as “internal electrodes”.
  • the first internal electrode 41 is electrically connected to the first external electrode 31 at the first end face 21 of the ceramic body 2, and the second internal electrode 42 is the second end face 22 of the ceramic body 2. And electrically connected to the second external electrode 32.
  • the first internal electrode 41 extends from the first end face 21 of the ceramic body 2 toward the second end face 22, and the second internal electrode 42 extends from the second end face 22 of the ceramic body 2.
  • the first internal electrodes 41 and the second internal electrodes 42 are alternately arranged so as to face each other inside the ceramic body 2.
  • the number of internal electrodes (the total of the first internal electrode 41 and the second internal electrode 42) may be, for example, about 2 or more and 50 or less.
  • the distance between the adjacent first internal electrode 41 and second internal electrode 42 is not particularly limited, and can be appropriately set according to a desired application.
  • the distance between the adjacent first internal electrode 41 and second internal electrode 42 may be, for example, about 10 ⁇ m to 200 ⁇ m.
  • the composition of the internal electrode is not particularly limited, and may be set as appropriate according to the application.
  • the first internal electrode 41 and the second internal electrode 42 may be, for example, Ni electrodes that exhibit good ohmic properties with respect to a barium titanate-based semiconductor.
  • a glass layer 5 may be formed on the surface of the ceramic body 2 as shown in FIG.
  • the glass layer 5 has a function of improving environmental resistance and element strength.
  • the composition and thickness of the glass layer 5 are not particularly limited, and may be set as appropriate according to the application.
  • the first internal electrode 41 and the second internal electrode 42 are disposed inside the ceramic body 2, but the semiconductor element 1 according to the present embodiment is limited to this configuration. However, the configuration may be such that no internal electrode is provided.
  • plating layers 61 and 62 (described later) are formed on the surfaces of the first external electrode 31 and the second external electrode 32.
  • the semiconductor element 1 according to the present embodiment is It is not limited to this structure, The structure which does not have a plating layer may be sufficient.
  • the semiconductor element 1 includes a first external electrode 31 disposed on the first end surface 21 of the ceramic body 2 and a second external surface disposed on the second end surface 22 of the ceramic body 2. Electrode 32.
  • the first external electrode 31 and the second external electrode 32 may be formed so as to extend to a part of the side surface of the ceramic body 2 as shown in FIG.
  • the “side surface” of the ceramic body 2 refers to a surface other than the first end surface 21 and the second end surface 22 of the ceramic body 2.
  • the first external electrode 31 and the second external electrode 32 may be collectively referred to as “external electrode”.
  • the composition and configuration of the external electrode can be appropriately set according to the type of the ceramic body 2 or the internal electrodes (the first internal electrode 41 and the second internal electrode 42) when present.
  • the first external electrode 31 and the second external electrode 32 may have, for example, a multilayer structure in which NiCr, NiCu alloy, and Ag are sequentially stacked.
  • plating layers 61 and 62 may be formed on the surfaces of the first external electrode 31 and the second external electrode 32 as shown in FIG.
  • the plating layers 61 and 62 have a function of improving solder wettability and heat resistance during mounting.
  • the composition of the plating layers 61 and 62 can be appropriately selected according to the composition of the external electrode, and may be, for example, a Sn plating layer, a Ni plating layer, or a combination of two or more thereof.
  • the first internal electrode 41 and the second internal electrode 42 are disposed inside the ceramic body 2, but the semiconductor element 1 according to the present embodiment is limited to this configuration. However, the configuration may be such that no internal electrode is provided.
  • the glass layer 5 is formed on the surface of the ceramic body 2, but the semiconductor element 1 according to the present embodiment is not limited to this configuration. The structure which does not have may be sufficient.
  • the method for manufacturing a semiconductor device includes a step of preparing perovskite type compound particles, a step of forming a green chip containing perovskite type compound particles, and a step of obtaining a ceramic body by firing the green chip. And forming a semiconductor element by forming external electrodes on both end faces of the ceramic body.
  • a method for manufacturing a stacked PTC thermistor having an internal electrode will be mainly described.
  • the method for manufacturing a semiconductor element according to the present invention is not limited to the following method. Absent.
  • perovskite compound particles containing at least Ba and Ti are prepared as raw materials for the ceramic body constituting the semiconductor element.
  • the perovskite type compound particles as the raw material may contain at least one element selected from the group consisting of rare earth elements excluding Pm, Tm, Yb and Lu and / or Nb, W, Sb and Ta in addition to Ba and Ti. It may contain at least one element selected from the group consisting of:
  • Each raw material of the perovskite type compound particles is weighed so that the composition of the ceramic sintered body particles contained in the ceramic body constituting the finally obtained semiconductor element becomes the target composition.
  • the composition of the target ceramic sintered body particles is as follows.
  • ICP-AES Inductively-Coupled-Plasma-Atomic-Emission-Spectrometry
  • It may be a composition represented by the formula (1).
  • ⁇ is at least one element selected from the group consisting of rare earth elements excluding Pm, Tm, Yb and Lu, and ⁇ is at least one selected from the group consisting of Nb, W, Sb and Ta Elements.
  • m Ba is 99.50 ⁇ m Ba ⁇ 100.5
  • the range of m ( ⁇ + ⁇ ) is 0.020 ⁇ m ( ⁇ + ⁇ ) ⁇ 0.500
  • m is 0.995 ⁇ m ⁇ 1.005.
  • the ceramic sintered body particles contained in the ceramic body constituting the finally obtained semiconductor element contain the elements ⁇ and / or ⁇ as donors (semiconductor agents).
  • the raw material perovskite type compound particles may contain neither element ⁇ nor element ⁇ , or the total amount of element ⁇ and / or element ⁇ necessary for obtaining ceramic sintered particles having a desired composition may be included. It does not have to be included.
  • the amount of element ⁇ and / or ⁇ chloride, hydroxide, oxide, carbonate, alkoxide, ionized aqueous solution, etc. necessary for preparation of the ceramic slurry described later can be adjusted to the desired composition. it can.
  • the method for preparing the raw material perovskite type compound particles is not particularly limited, and a solid-phase synthesis method or a hydrothermal synthesis method such as a hydrothermal synthesis method or an oxalic acid method is appropriately used depending on the desired specific surface area and c / a. You can choose.
  • the raw material perovskite type compound particles may be prepared, for example, by the procedure described below. Each of the above-mentioned raw materials weighed is put into a ball mill together with PSZ (partially stabilized zirconia) balls and pure water. At this time, a sintering aid such as SiO 2 may be added as appropriate.
  • the raw materials in the ball mill are sufficiently mixed and pulverized by a wet process and dried to obtain a mixed powder.
  • the mixed powder is calcined at a temperature of 800 ° C. or higher and 1100 ° C. or lower to obtain raw material perovskite type compound particles as calcined powder.
  • the calcination temperature can be appropriately set according to the specific surface area of the target perovskite type compound particles and the value of c / a.
  • the specific surface area of the raw material perovskite compound particles is preferably 4.0 m 2 / g or more and 14.0 m 2 / g or less.
  • the specific surface area is 4.0 m 2 / g or more
  • the ceramic sintered body particles in the ceramic body constituting the obtained semiconductor element can be made a small particle diameter having an average particle diameter of 1.0 ⁇ m or less.
  • the specific surface area is 14.0 m 2 / g or less, the number of grain boundaries between the sintered particles in the ceramic body can be reduced, and the contact ratio of the sintered particles can be increased. As a result, the specific resistance at room temperature of the semiconductor element can be lowered.
  • the specific surface area of the perovskite compound particles is more preferably 4.0 m 2 / g or more and 11.0 m 2 / g or less. When the specific surface area is 11.0 m 2 / g or less, the specific resistance value at room temperature of the obtained semiconductor element can be further reduced.
  • the specific surface area of the perovskite compound particles can be measured by a gas adsorption method such as a BET method.
  • Raw material perovskite type compound particles have a highly tetragonal crystal structure.
  • perovskite type compound particles having a highly tetragonal crystal structure As a raw material, the specific resistance of the semiconductor element at room temperature (25 ° C.) can be lowered.
  • the ratio c / a of the c-axis length to the a-axis length of the crystal lattice of the raw material perovskite compound particles is preferably 1.005 or more and 1.009 or less.
  • c / a is more preferably 1.006 or more and 1.009 or less.
  • the c / a of the raw material perovskite compound particles can be calculated by conducting a qualitative analysis using a powder X-ray diffractometer and performing a Rietveld analysis.
  • the raw material perovskite type compound particles contain one or more rare earth elements as donors.
  • a green chip containing raw material perovskite type compound particles is formed.
  • a step of forming a green chip containing perovskite compound particles includes a step of producing a ceramic green sheet containing perovskite compound particles, and a main part of the ceramic green sheet.
  • a step of applying a conductive paste for internal electrodes on a surface a step of obtaining a laminate by laminating a plurality of ceramic green sheets coated with a conductive paste for internal electrodes, and a conductivity for internal electrodes above and below the laminate. And placing a ceramic green sheet to which a paste has not been applied, press-bonding, and cutting to a predetermined size to obtain a green chip.
  • a ceramic green sheet containing perovskite type compound particles is prepared according to the following procedure.
  • An organic binder, a dispersant and water are added to the raw material perovskite type compound particles and mixed with zirconia balls for several hours to obtain a ceramic slurry.
  • the raw material perovskite type compound particles do not contain both element ⁇ and element ⁇ , or the total amount of element ⁇ and / or element ⁇ necessary for obtaining ceramic sintered particles having a desired composition
  • a predetermined amount of chloride, hydroxide, oxide, carbonate, alkoxide, ionized aqueous solution, or the like of the element ⁇ and / or ⁇ may be added as a donor during the preparation of the ceramic slurry.
  • the above-mentioned ceramic slurry is formed into a sheet by the doctor blade method and dried to produce a ceramic green sheet.
  • the thickness of the ceramic green sheet is preferably 10 ⁇ m or more and 50 ⁇ m or less.
  • a conductive paste for internal electrodes is applied on the main surface of the ceramic green sheet.
  • conductive powder such as metal powder and an organic binder are dispersed in an organic solvent to prepare a conductive paste for internal electrodes.
  • metal powder such as Ni metal powder can be appropriately used.
  • this internal electrode conductive paste on the main surface of the ceramic green sheet.
  • the coating thickness of the internal electrode conductive paste is set so that the thickness of the internal electrode in the finally obtained semiconductor element is 0.5 ⁇ m or more and 2 ⁇ m or less.
  • the conductive paste for internal electrodes may be applied by a method such as screen printing.
  • a plurality of ceramic green sheets coated with the internal electrode conductive paste are laminated to obtain a laminate.
  • the number of laminated ceramic green sheets coated with the internal electrode conductive paste may be set according to the number of internal electrodes that the finally obtained semiconductor element should have.
  • ceramic green sheets not coated with the internal electrode conductive paste are disposed on and under the laminate, for example, 20 sheets at a time, and subjected to pressure bonding, with predetermined dimensions so that the dimensions after firing become a desired value. Cut to get green chips.
  • the size of the ceramic body obtained by firing the green chip may be, for example, L size 2.0 mm ⁇ W size 1.2 mm ⁇ T size 1.0 mm.
  • a plurality of ceramic green sheets not coated with the internal electrode conductive paste are stacked, pressed, and cut to a predetermined size to produce a green chip. It's okay.
  • the ceramic body is obtained by firing the green chip.
  • the green chip is degreased at a temperature of 300 ° C. to 450 ° C. for 10 hours to 15 hours in an air atmosphere.
  • the green chip after the degreasing treatment is 0 at a temperature of 1000 ° C. or higher and 1300 ° C. or lower in a reducing atmosphere such as H 2 / N 2 / H 2 O mixed gas, Ar / H 2 , N 2 / H 2 / H 2 O, or the like. Baking for 5 hours or more and 3 hours or less to obtain a ceramic body.
  • the obtained ceramic body is glass-coated and heat-treated at a temperature of 600 ° C. or more and 900 ° C. or less in an air atmosphere to form a glass layer on the surface of the ceramic body, and at the same time, Reoxidation may be performed.
  • external electrodes are formed on both end faces of the ceramic body.
  • the ceramic body is barrel-polished.
  • External electrodes are formed on both end faces of the ceramic body after barrel polishing.
  • the composition and formation method of the external electrode are not particularly limited, and can be appropriately selected according to the purpose.
  • the external electrode can be formed by sputtering Cr, NiCu alloy and Ag in this order on both end faces of the ceramic body.
  • the external electrode may be formed by applying a paste containing a resin component and a metal (such as Ag) and baking it at an appropriate temperature.
  • a plating layer may be formed on the surface of the formed external electrode by a method such as electrolytic plating.
  • the composition of the plating layer can be appropriately selected according to the composition of the external electrode, and may be, for example, a Sn plating layer, a Ni plating layer, or a combination of two or more thereof. In this way, the semiconductor element according to this embodiment is obtained.
  • the semiconductor elements of Comparative Examples 1 and 2 and Examples 1 to 9 were produced by the following procedure.
  • the semiconductor elements of Comparative Examples 1 and 2 and Examples 1 to 9 are all laminated PTC thermistors.
  • Each of the above-mentioned raw materials weighed was put into a ball mill together with PSZ (partially stabilized zirconia) balls and pure water, sufficiently mixed and pulverized in a wet manner, and dried to obtain a mixed powder.
  • This mixed powder was calcined at a temperature of 800 ° C. or higher and 1100 ° C. or lower to obtain raw material perovskite type compound particles as calcined powder.
  • the obtained perovskite compound particles had a specific surface area of 2.1 m 2 / g and c / a of 1.010.
  • the specific surface area of the raw material perovskite type compound particles was measured using a Macsorb (registered trademark) manufactured by Mountec Co., Ltd.
  • the c / a of the raw material perovskite type compound particles was determined by conducting a qualitative analysis using a powder X-ray diffraction apparatus (RINT2500 manufactured by Rigaku Corporation) and performing a Rietveld analysis.
  • An organic binder, a dispersant and water were added to the obtained raw material perovskite type compound particles and mixed with zirconia balls for several hours to obtain a ceramic slurry.
  • This ceramic slurry was formed into a sheet by a doctor blade method and dried to prepare a ceramic green sheet having a thickness of 30 ⁇ m.
  • Ni metal powder and an organic binder were dispersed in an organic solvent to prepare a conductive paste for internal electrodes.
  • This internal electrode conductive paste was applied on the main surface of the ceramic green sheet by screen printing.
  • the coating thickness of the internal electrode conductive paste was adjusted so that the thickness of the internal electrode in the finally obtained semiconductor element was 0.5 ⁇ m or more and 2 ⁇ m or less.
  • the ceramic green sheet coated with the internal electrode conductive paste and the ceramic green sheet not coated with the internal electrode conductive paste are included so that 24 internal electrodes are included and the distance between the internal electrodes is 30 ⁇ m. To obtain a laminate.
  • This green chip was degreased at 300 ° C. for 12 hours in an air atmosphere.
  • the green chip after the degreasing treatment was baked at a temperature of 1000 ° C. or higher and 1300 ° C. or lower for 2 hours in a reducing atmosphere using a H 2 / N 2 / H 2 O mixed gas to obtain a ceramic body.
  • the obtained ceramic body was glass-coated and heat-treated at a temperature of 800 ° C. or lower in an air atmosphere, thereby forming a glass layer on the surface of the ceramic body and simultaneously re-oxidizing the ceramic body.
  • the ceramic body on which the glass layer was formed was barrel polished. External electrodes were formed by sputtering Cr, NiCu alloy and Ag in this order on both end faces of the ceramic body after barrel polishing. An Sn plating layer was formed on the surface of the formed external electrode by electrolytic plating. In this way, a semiconductor element of Comparative Example 1 was obtained.
  • Comparative Example 2 and Examples 1 to 9 Semiconductor devices of Comparative Example 2 and Examples 1 to 9 were manufactured in the same procedure as Comparative Example 1 except that perovskite type compound particles having specific surface areas and c / a values shown in Table 1 described later were used as raw materials. .
  • the average particle diameter and contact rate of the ceramic sintered body particles were measured.
  • the average particle size of the sintered ceramic particles was measured by the following procedure. First, the semiconductor element is polished to about 1/2 W point (about half the W dimension of the semiconductor element) in the direction of the LT plane (plane perpendicular to the W direction), and the semiconductor element cross section parallel to the LT plane is exposed. I let you. This cross section was observed using a scanning electron microscope (Hitachi SU-8040) under the conditions of an acceleration voltage of 1 kV and a magnification of 10,000 times to obtain an SEM image.
  • the size of the region (observation region) observed by SEM was set to a size that allows counting of 80 to 200 ceramics sintered body particles.
  • This SEM image was subjected to image analysis using an analyzer (“A Image-kun” manufactured by Asahi Kasei Engineering Co., Ltd.), and the area of ceramic sintered body particles in the SEM image was determined.
  • An equivalent area equivalent circle diameter (Heywood diameter) calculated based on the obtained area was defined as the particle diameter of the ceramic sintered body particles.
  • the average value of the particle diameters of the ceramic sintered body particles completely contained in the observation region was defined as the average particle diameter of the ceramic sintered body particles.
  • the average particle diameter of the ceramic sintered body particles was obtained in the above-mentioned semiconductor element cross section, but the same result can be obtained even when the average particle diameter is obtained in other semiconductor element cross sections. You can think of it.
  • the contact ratio of the ceramic sintered body particles was measured using the same cross section as that of the semiconductor element used for obtaining the average particle diameter.
  • the portion sandwiched between the internal electrodes in the vicinity of the central portion of the ceramic body 2 was observed with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the cross section to be observed with the SEM is not particularly limited, and an arbitrary cross section may be selected.
  • the cross section is obtained by, for example, polishing the semiconductor element 1 in the LT plane (plane perpendicular to the W direction) to about 1/2 W point (about half the W dimension of the semiconductor element).
  • the cross section of the semiconductor element may be parallel to.
  • the region to be observed with the SEM is not particularly limited, but may be, for example, a region sandwiched between internal electrodes in the vicinity of the central portion of the ceramic body 2.
  • the dimension of the observation region of SEM was set to a dimension that allows the number of sintered ceramic particles to be counted from 80 to 200 at an observation magnification of 10,000.
  • the resulting SEM image, and image analysis using an analysis apparatus manufactured by Asahi Kasei Engineering Corporation "A picture kun"
  • the total L G around the length of the ceramic sintered particles present in the observation region, the observation region The total peripheral length L NC of the pores existing inside and the outer peripheral length L S of the observation region were determined.
  • Examples of the results of obtaining L G , L NC and L S by image analysis are shown in FIGS. 4 to 6, respectively.
  • the following formula was used to determine the contact ratio of the ceramic sintered body particles.
  • the average particle diameter of the ceramic sintered body particles contained in the obtained semiconductor element can be 0.4 ⁇ m or more and 1.0 ⁇ m or less, and the contact ratio of the ceramic sintered body particles is 45% or more. I understand that I was able to.
  • Comparative Example 1 in which the specific surface area of the raw material perovskite compound particles was less than 4.0 m 2 / g and c / a was greater than 1.009, the ceramic sintered body contained in the obtained semiconductor element The average particle diameter of the particles was larger than 1.0 ⁇ m, and the contact ratio of the ceramic sintered body particles was less than 45%. Further, in Comparative Example 2 in which the specific surface area of the raw material perovskite compound particles was less than 4.0 m 2 / g, the contact ratio of the ceramic sintered body particles contained in the obtained semiconductor element was less than 45%. It was.
  • the semiconductor elements of Examples 1 to 9 in which the average particle size of the sintered ceramic particles was 0.4 ⁇ m or more and 1.0 ⁇ m or less and the contact rate was 45% or more were 71 ⁇ at room temperature.
  • the specific resistance value was as low as cm or less.
  • the semiconductor elements of Examples 1 to 9 had high withstand voltage characteristics of 1000 V / mm or more.
  • the semiconductor element of Comparative Example 1 in which the average particle diameter of the ceramic sintered body particles was larger than 1.0 ⁇ m and the contact rate was less than 45% had low withstand voltage characteristics of less than 1000 V / mm.
  • the semiconductor element of Comparative Example 2 in which the contact ratio of the ceramic sintered body particles was less than 45% exhibited a high specific resistance value exceeding 80 ⁇ ⁇ cm at room temperature.
  • the semiconductor element according to the present invention has both a high withstand voltage characteristic and a low specific resistance value at room temperature, and can be suitably used in a wide range of applications.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Electromagnetism (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Thermistors And Varistors (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

L'invention concerne un élément semi-conducteur qui comprend : un élément en céramique qui contient des particules de céramique frittées ; et une première électrode externe et une deuxième électrode externe qui sont respectivement disposées sur les faces d'extrémité de l'élément en céramique. Les particules de céramique frittées sont constituées d'un composé de pérovskite qui contient au moins du Ba et du Ti, et ont un diamètre moyen de particule compris entre 0,4 et 1,0 μm. Lorsqu'une région dans une section transversale de l'élément semi-conducteur est sélectionnée et observée avec un microscope électronique à balayage, le rapport de contact des particules de céramique frittées, tel que calculé sur la base du total des longueurs périphériques des particules de céramique frittées présentes à l'intérieur de la région, du total des longueurs périphériques des pores présents à l'intérieur de la région, de la longueur périphérique extérieure de la région et des longueurs de contact des particules de céramique frittées présentes à l'intérieur de la région est de 45 % ou plus.
PCT/JP2016/050205 2015-02-06 2016-01-06 Élément semi-conducteur et son procédé de fabrication WO2016125520A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE112016000618.7T DE112016000618T5 (de) 2015-02-06 2016-01-06 Halbleiterelement und Verfahren zur Fertigung desselben
JP2016573240A JP6739353B2 (ja) 2015-02-06 2016-01-06 半導体素子およびその製造方法
CN201680007338.7A CN107210105B (zh) 2015-02-06 2016-01-06 半导体元件及其制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015022350 2015-02-06
JP2015-022350 2015-02-06

Publications (1)

Publication Number Publication Date
WO2016125520A1 true WO2016125520A1 (fr) 2016-08-11

Family

ID=56563872

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/050205 WO2016125520A1 (fr) 2015-02-06 2016-01-06 Élément semi-conducteur et son procédé de fabrication

Country Status (4)

Country Link
JP (1) JP6739353B2 (fr)
CN (1) CN107210105B (fr)
DE (1) DE112016000618T5 (fr)
WO (1) WO2016125520A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3535739B1 (fr) 2016-12-06 2020-10-28 MACO Technologie GmbH Dispositif de sécurité pour surveiller la position d'un ouvrant

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07220902A (ja) * 1994-02-07 1995-08-18 Murata Mfg Co Ltd チタン酸バリウム系半導体磁器
JP2001031471A (ja) * 1999-05-20 2001-02-06 Murata Mfg Co Ltd チタン酸バリウム系半導体セラミック粉末および積層型半導体セラミック素子

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001326102A (ja) * 2000-05-15 2001-11-22 Murata Mfg Co Ltd 積層型半導体セラミック素子およびその製造方法
JP4211510B2 (ja) * 2002-08-13 2009-01-21 株式会社村田製作所 積層型ｐｔｃサーミスタの製造方法
EP2439181A4 (fr) * 2009-06-05 2018-03-28 Murata Manufacturing Co., Ltd. Composition de céramique de semi-conducteur à base de titanate de baryum et élément en céramique de semi-conducteur à base de titanate de baryum

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07220902A (ja) * 1994-02-07 1995-08-18 Murata Mfg Co Ltd チタン酸バリウム系半導体磁器
JP2001031471A (ja) * 1999-05-20 2001-02-06 Murata Mfg Co Ltd チタン酸バリウム系半導体セラミック粉末および積層型半導体セラミック素子

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3535739B1 (fr) 2016-12-06 2020-10-28 MACO Technologie GmbH Dispositif de sécurité pour surveiller la position d'un ouvrant

Also Published As

Publication number Publication date
JPWO2016125520A1 (ja) 2017-09-14
CN107210105B (zh) 2019-09-03
DE112016000618T5 (de) 2017-11-02
JP6739353B2 (ja) 2020-08-12
CN107210105A (zh) 2017-09-26

Similar Documents

Publication Publication Date Title
CN108735508B (zh) 多层陶瓷电容器及其制造方法
CN109326442B (zh) 多层陶瓷电容器及其制造方法
TWI402872B (zh) 電介質瓷器及疊層陶瓷電容器以及它們的製造方法
JP5067401B2 (ja) 誘電体セラミックおよびその製造方法ならびに積層セラミックコンデンサ
KR102363231B1 (ko) 적층 세라믹 콘덴서, 세라믹 분말, 및 그들의 제조 방법
JP7131955B2 (ja) 積層セラミックコンデンサおよびその製造方法
JPH11273986A (ja) 誘電体セラミックおよびその製造方法、ならびに、積層セラミック電子部品およびその製造方法
JP6900157B2 (ja) 積層セラミックコンデンサ
CN112216510B (zh) 陶瓷电子器件及其制造方法
JPH11273985A (ja) 誘電体セラミックおよびその製造方法、ならびに、積層セラミック電子部品およびその製造方法
JP6523930B2 (ja) 誘電体磁器組成物及びこれを含む積層セラミックキャパシタ
CN110776317B (zh) 电介质陶瓷组合物及层叠陶瓷电子部件
WO2013022064A1 (fr) Céramique diélectrique, pièce électronique céramique à couches, condensateur céramique à couches et procédé pour la production d'un condensateur céramique à couches
TW201821387A (zh) 介電體磁器組成物及陶瓷電子零件
KR20080109643A (ko) 적층형 ｐｔｃ 서미스터 및 이의 제조방법
JP6394702B2 (ja) チップ型セラミック半導体電子部品
JP4710096B2 (ja) 積層型正特性サーミスタ
JP6636744B2 (ja) 誘電体磁器組成物及びこれを用いた電子素子
JP4780306B2 (ja) 積層型サーミスタ及びその製造方法
JP2015222780A (ja) 圧電セラミックス、その製造方法及び圧電体素子
JP6739353B2 (ja) 半導体素子およびその製造方法
JPH06151103A (ja) 積層型半導体磁器組成物
JP4710097B2 (ja) 積層型正特性サーミスタ
CN115403367A (zh) 电介质组合物及层叠陶瓷电子部件
JP7021701B2 (ja) セラミック部材及び電子素子

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: 16746351

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016573240

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 112016000618

Country of ref document: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16746351

Country of ref document: EP

Kind code of ref document: A1