WO2016125519A1 - Élément semi-conducteur et son procédé de fabrication - Google Patents

Élément semi-conducteur et son procédé de fabrication Download PDF

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Publication number
WO2016125519A1
WO2016125519A1 PCT/JP2016/050204 JP2016050204W WO2016125519A1 WO 2016125519 A1 WO2016125519 A1 WO 2016125519A1 JP 2016050204 W JP2016050204 W JP 2016050204W WO 2016125519 A1 WO2016125519 A1 WO 2016125519A1
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ceramic
semiconductor element
particles
sintered body
internal electrode
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PCT/JP2016/050204
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English (en)
Japanese (ja)
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渉 青戸
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株式会社村田製作所
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    • 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
    • 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

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 semiconductor porcelain characterized in that, in a BaTiO 3 -based semiconductor ceramic subjected to reduction firing reoxidation, the sintered density is 85 to 90% relative density. . Patent Document 1 describes that sufficient PTC characteristics can be obtained by appropriately reducing the sintered density, and that the particle size of the semiconductor ceramic is preferably 0.5 to 2 ⁇ m.
  • Patent Document 2 discloses a barium titanate semiconductor ceramic having an average ceramic particle size of 0.9 ⁇ m or less. Patent Document 2 describes that a barium titanate-based semiconductor ceramic having an average ceramic particle size in the above range has a small specific resistance at room temperature and an excellent withstand voltage strength. Patent Document 2 discloses that the above-described 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 2). However, as a result of repeated studies by the present inventor, it has been found that there is a problem that the operating temperature of the PTC thermistor decreases due to the formation of fine particles.
  • An object of the present invention is to provide a semiconductor device having high withstand voltage characteristics and a high operating temperature, and a method for manufacturing the same.
  • the present inventor reduced the Curie point of the ceramic sintered body particles by making the ceramic sintered body particles contained in the ceramic body constituting the PTC thermistor fine, and as a result, the operating temperature of the PTC thermistor decreased. I paid attention to it.
  • perovskite-type barium titanate compound particles with high tetragonal properties as raw materials, even if the ceramic sintered particles are made fine particles to improve the withstand voltage characteristics, It has been found that the reduction of the point can be suppressed and a high operating temperature can be achieved, and the present invention has been completed.
  • 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 1.0 ⁇ m or less, A semiconductor element is provided in which the ratio c / a of the c-axis length to the a-axis length of the crystal lattice of the ceramic sintered body particles is 1.007 or more.
  • the average particle diameter of the ceramic sintered body particles described above is preferably 0.6 ⁇ m or more and 0.9 ⁇ m or less. Further, the ratio (tetragonal) c / a of the c-axis length to the a-axis length of the crystal lattice of the ceramic sintered body particles described above is preferably 1.008 or more and 1.010 or less.
  • the Curie point of the ceramic sintered body particles described above can be 100 ° C. or higher.
  • 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 2.9 m 2 / g or more and 13.0 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 not less than 1.006 and not more than 1.010.
  • 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 high operating temperature by having 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 high operating 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.
  • 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 contain Zr that may be inevitably 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 include 0.010 mol part or more and 0.600 mol part or less of Zr.
  • the average particle diameter of the ceramic sintered body particles contained in the ceramic body 2 is 1.0 ⁇ m or less.
  • the semiconductor device 1 can achieve high withstand voltage characteristics.
  • the average particle diameter of the ceramic sintered body particles is preferably 0.6 ⁇ m or more and 0.9 ⁇ m or less.
  • the average particle size is 0.6 ⁇ m or more, the specific resistance of the ceramic body can be reduced, and consequently the resistance value of the semiconductor element can be reduced.
  • the average particle size is 0.9 ⁇ m or less, the withstand voltage characteristics of the semiconductor element 1 can be further improved.
  • 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 ratio c / a of the c-axis length to the a-axis length of the crystal lattice of the ceramic sintered body particles contained in the ceramic body 2 is 1.007 or more.
  • c / a is 1.007 or more, a high Curie point can be maintained even when the average particle size of the ceramic sintered body particles is small, and as a result, a semiconductor element 1 having a high operating temperature is obtained. be able to.
  • the ratio c / a of the c-axis length to the a-axis length of the crystal lattice of the ceramic sintered body particles is preferably 1.008 or more and 1.010 or less.
  • the Curie point of the ceramic sintered body particles can be further increased.
  • the ceramic body 2 is composed of a barium titanate material
  • c / a is generally 1.010 or less.
  • the c / a of the sintered ceramic particles can be calculated by performing a qualitative analysis using a powder X-ray diffractometer and performing a Rietveld analysis. In the present specification, it may be considered that the c / a measurement value of the ceramic sintered body particles is substantially the same as the c / a measurement value of the ceramic body 2.
  • the Curie point of the ceramic sintered body particles contained in the ceramic body 2 can be 100 ° C. or higher.
  • the semiconductor element 1 can be used in an operating temperature range of 85 ° C., which is generally required in the market of in-vehicle thermistors, even when variation in the Curie point of each product is taken into consideration. Can be suitably used.
  • the Curie point of ceramic sintered body particles can be determined by differential scanning calorimetry (DSC). In the present specification, the measured value of the Curie temperature of the ceramic sintered body particles may be considered to be substantially the same as the measured value of the Curie temperature of the ceramic body 2.
  • 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 Cr, 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.
  • 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.
  • 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, sufficiently mixed and pulverized in a wet manner, and dried to obtain a mixed powder.
  • PSZ partially stabilized zirconia
  • raw material perovskite type compound particles are obtained.
  • 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 2.9 m 2 / g or more and 13.0 m 2 / g or less.
  • the specific surface area is 2.9 m 2 / g or more, the ceramic sintered body particles in the ceramic body constituting the semiconductor element to be obtained can be reduced to an average particle size of 0.9 ⁇ m or less.
  • a high withstand voltage characteristic of 1000 V / mm or more can be obtained.
  • the specific surface area is 13.0 m 2 / g or less, the Curie point of the ceramic sintered body particles in the ceramic body constituting the obtained semiconductor element can be set to 100 ° C. or higher.
  • the specific surface area of the perovskite compound particles is more preferably 2.9 m 2 / g or more and 7.8 m 2 / g or less. When the specific surface area is 7.8 m 2 / g or less, a high Curie temperature of 110 ° C. or more is obtained.
  • 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.
  • the ceramic sintered body particles in the ceramic body constituting the obtained semiconductor element have a tetragonal structure.
  • 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 from 1.006 to 1.010.
  • the c / a of the ceramic sintered body particles in the ceramic body constituting the obtained semiconductor element can be made 1.007 or more.
  • the Curie point of the body particles can be set to 100 ° C. or higher.
  • c / a is generally 1.010 or less.
  • c / a is more preferably 1.007 or more and 1.010 or less.
  • the Curie point of the ceramic sintered body particles can be 110 ° C. or more.
  • 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.
  • 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 20 ⁇ m or more and 40 ⁇ 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 placed on the top and bottom of the laminate, for example, 5 sheets each, and pressed, and predetermined dimensions are set 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 250 ° C. to 350 ° C. for 10 hours to 15 hours in an air atmosphere.
  • the green chip after the degreasing treatment is 0.5 hours to 3 hours at a temperature of 1050 ° C. or higher and 1240 ° C. or lower in a reducing atmosphere such as N 2 / H 2 , Ar / H 2 , N 2 / H 2 / H 2 O
  • firing is performed to obtain a ceramic body.
  • the obtained ceramic body is glass-coated and heat-treated at a temperature of 600 ° C. or higher and 900 ° C. or lower in an air atmosphere to form a glass layer on the surface of the ceramic body, and at the same time, recycle the ceramic body. Oxidation 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 (Ag or the like) 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 Examples 1 to 19 were fabricated by the following procedure.
  • the semiconductor elements of Examples 1 to 19 are stacked PTC thermistors.
  • perovskite type compound particles were prepared as raw materials.
  • 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. under a degassing temperature of 250 ° C.
  • 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.
  • coated the conductive paste for internal electrodes was laminated
  • This green chip was degreased at 300 ° C. for 12 hours in an air atmosphere.
  • the green chip after the degreasing treatment was fired for 2 hours at a temperature of 1050 ° C. or higher and 1240 ° C. or lower in a reducing atmosphere of N 2 / H 2 to obtain a ceramic body.
  • the obtained ceramic body was glass-coated and heat-treated at 800 ° C. in an air atmosphere to form a glass layer on the surface of the ceramic body and simultaneously re-oxidize 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. Thus, the semiconductor element of Example 1 was obtained.
  • Example 2 to 19 Semiconductor devices of Examples 2 to 19 were produced in the same procedure as 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, c / a, and Curie point 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 (JSM-7500FA manufactured by JEOL Ltd.) under the conditions of an acceleration voltage of 5 kV and a magnification of 10,000 times to obtain an SEM image.
  • JSM-7500FA manufactured by JEOL Ltd.
  • the SEM image was subjected to image analysis using an analyzer (IP-1000 manufactured by Asahi Engineering Co., Ltd.), and the area of the 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 field of view of the observed SEM image (about 18 ⁇ m square or more and about 20 ⁇ m square or less) 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 c / a of the ceramic sintered body particles was determined by performing a qualitative analysis using a powder X-ray diffraction apparatus (RINT2500 manufactured by Rigaku Corporation) and performing a Rietveld analysis.
  • the Curie point of the sintered ceramic particles was determined by DSC measurement using a differential scanning calorimeter (model DSC2920) manufactured by TA Instruments.
  • the DSC measurement was performed under the conditions that the measurement atmosphere was an air atmosphere, the rate of temperature increase was 10 ° C./min, the start temperature was 25 ° C., and the end temperature was 250 ° C.
  • the peak temperature of the endothermic peak in the obtained differential heat-temperature curve was taken as the Curie point.
  • the withstand voltage characteristics were measured by the following procedure. After mounting the semiconductor element on the substrate, a voltage of 680 V / mm was applied to the semiconductor element for 3 minutes, and the current value at that time was measured. Next, when the semiconductor element was not destroyed at a voltage of 680 V / mm, the measurement was repeated by increasing the voltage in steps of 20 V / mm and applying it for 3 minutes. The voltage value immediately before the semiconductor element was destroyed was defined as a withstand voltage characteristic. The above measurement results are shown in Table 1.
  • the semiconductor elements of Examples 13, 16, 18 and 19 in which c / a of the ceramic sintered body particles was less than 1.007 the Curie point of the ceramic sintered body particles was less than 100 ° C. Therefore, it can be seen that the semiconductor elements of Examples 18 and 19 had a low operating temperature of less than 100 ° C.
  • the semiconductor elements of Examples 1 and 2 in which the average particle diameter of the ceramic sintered body particles was larger than 1.0 ⁇ m exhibited low withstand voltage characteristics of less than 1000 V / mm.
  • the semiconductor element according to the present invention has both a high withstand voltage characteristic and a high operating temperature, and can be suitably used in an operating temperature range of 85 ° C. generally required in the in-vehicle thermistor market.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thermistors And Varistors (AREA)

Abstract

L'invention concerne un élément semi-conducteur qui comprend : un élément en céramique qui contient des particules de céramique frittée; une première électrode externe qui est disposée sur une première face d'extrémité de l'élément en céramique; et une seconde électrode externe qui est disposée sur une seconde face d'extrémité de l'élément en céramique. Les particules de céramique frittée sont constituées d'un composé de pérovskite qui contient au moins du Ba et du Ti, et ont un diamètre des particules moyen de 1,0 µm ou moins. Le rapport de la longueur de l'axe c sur la longueur de l'axe a du réseau cristallin des particules de céramique frittée, c'est-à-dire c/a, est de 1,007 ou plus.
PCT/JP2016/050204 2015-02-06 2016-01-06 Élément semi-conducteur et son procédé de fabrication WO2016125519A1 (fr)

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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

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

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