EP1993108B1 - Composition de matériau doté d'une microstructure noyau-enveloppe utilisé pour un varistor - Google Patents

Composition de matériau doté d'une microstructure noyau-enveloppe utilisé pour un varistor Download PDF

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Publication number
EP1993108B1
EP1993108B1 EP07108464.4A EP07108464A EP1993108B1 EP 1993108 B1 EP1993108 B1 EP 1993108B1 EP 07108464 A EP07108464 A EP 07108464A EP 1993108 B1 EP1993108 B1 EP 1993108B1
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EP
European Patent Office
Prior art keywords
glass
varistor
cored
semi
material composition
Prior art date
Legal status (The legal status 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 status listed.)
Not-in-force
Application number
EP07108464.4A
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German (de)
English (en)
Other versions
EP1993108A1 (fr
Inventor
Ching-Hohn Lien
Chen-Tsung Kuo
Jun-Nan Lin
Jie-An Zhu
Li-Yun Zhang
Wei-Chang Lien
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Bee Fund Biotechnology Inc
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Bee Fund Biotechnology Inc
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Classifications

    • 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
    • H01C7/10—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 voltage responsive, i.e. varistors
    • H01C7/105—Varistor cores
    • 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
    • H01C7/10—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 voltage responsive, i.e. varistors
    • H01C7/105—Varistor cores
    • H01C7/108—Metal oxide
    • 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
    • H01C7/10—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 voltage responsive, i.e. varistors
    • H01C7/105—Varistor cores
    • H01C7/108—Metal oxide
    • H01C7/112—ZnO type
    • 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
    • H01C7/10—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 voltage responsive, i.e. varistors
    • H01C7/105—Varistor cores
    • H01C7/108—Metal oxide
    • H01C7/115—Titanium dioxide- or titanate type

Definitions

  • the present invention relates to a powderized material composition for a varistor according to the preamble portion of claim 1; and a method for manufacturing a varistor from said powedrized material composition.
  • varistors or surge absorbers are conventionally used in high-frequency applications for protecting IC from getting damaged due to overvoltage.
  • a silicon diode provides surge absorbent ability relying on the PN interface.
  • a varistor made from this material disadvantageously possesses relatively higher breakdown voltage and inferior surge absorbent ability.
  • Varistors constructed of Fe 2 O 3 and BaTiO 3 have the surge absorbent ability relying on the interface between electrodes and ceramics. However, such varistors present inferior electrical properties and are unsuitable for making high-voltage components.
  • the surge absorbent ability of varistors made from ZnO, TiO 2 , SnO 2 or SrTiO 3 typically depends on the interface between semi-conductive grains and grain-boundary insulating layers.
  • the grain-boundary insulating layers are primarily composed of crystalline phases, such as crystalline phases of ⁇ -Bi 2 O 3 , Na 2 O or SrTiO 3 .
  • the disadvantage of such varistors is that the production of the grain-boundary insulating layers requires sintering at a relatively higher temperature.
  • US 3,725,836 teaches making a varistor paste by dispersing a uniform mixture of glass frit powder and zinc oxide powder in a liquid vehicle. The liquid vehicle is removed in an electric furnace so that the glas frit fuses so as to bond the zinc oxide powder particles and to adhere firmly to an insulating base.
  • US 3,725,836 teaches two separate powder components that are mixed with each other to form a varistor layer. It is therefore not possible to control the distance between zinc oxide grains in the resulting ceramic.
  • the disclosed material composition has a core-shell microstructure at least comprising a cored-structure made of a conductive or semi-conductive material and a shelled-structure made from a glass material to wrap the cored-structure.
  • varistors constructed from the disclosed material composition can be produced through sintering the material composition at a relatively lower temperature, which is typically between 600°C and 1,100°C.
  • the electrical properties of such varistors can be decided and designated through adjusting some particular parameters such as the size and properties of the grain of the cored-structure, the thickness and insulation resistance of the insulating layer of the shelled-structure, and the interval between two parallel electrodes and the overlap area of the electrode materials of the varistors.
  • the novel material composition can be used for making both single-layered varistors and multiple-layered varistors, and the electrical properties of the varistors can be decided and designated during manufacturing for meeting various practical needs.
  • the present invention can be used for manufacturing varistors with desired voltage.
  • the method comprises sintering a novel material composition having a core-shell microstructure at a relatively lower temperature.
  • the shelled-structure of the novel material composition is made from a glass material which has almost no reaction with the material of the cored-structure of the material composition, electrical properties of such varistors can be decided and designed by precisely controlling the size and properties of the grain of the cored-structure, the thickness and insulation resistance of the insulating layer of the shelled-structure, and the interval between two parallel electrodes and the overlap area of the electrode materials of the varistors.
  • Fig. 1 is a schematic drawing of a varistor constructed of a novel material composition having a core-shell microstructure of the present invention.
  • the disclosed material composition 11 of the present invention has a core-shell microstructure which at least comprises a shelled-structure 12 and a cored-structure 14 wrapped by the shelled-structure 12.
  • the cored-structure 14 of the core-shell microstructure of the material composition 11 is made of a conductive or semi-conductive material
  • the shelled-structure 12 of the core-shell microstructure is made from a glass material that wraps the cored-structure 14.
  • the material composition 11 of the present invention may be in application of being manufactured into a ceramic component 20 for a varistor 10 through a standard ceramic processing.
  • the conductive material used as the cored-structure 14 of the core-shell microstructure of the material composition 11 of the present invention can be one of, a combination of two or more of or a combination of alloys of the metals selected from the group containing Fe, Al, Ni, Cu, Ag, Au, Pt and Pd.
  • the semi-conductive material used as the cored-structure 14 of the core-shell microstructure of the material composition 11 of the present invention can be one of, or a combination of two or more of the metals selected from the group containing ZnO, SrTiO 3 , BaTiO 3 , SiC, TiO 2 , SnO 2 , Si and GaAs.
  • the cored-structure 14 of the core-shell microstructure of the material composition 11 of the present invention can alternatively be made with a combination of the aforementioned conductive materials and semi-conductive materials.
  • the glass material used as the shelled-structure 12 of the core-shell microstructure of the material composition 11 of the present invention can be selected from the group containing silicate glass, boron glass, alumina-silica glass, phosphate glass and lead glass.
  • the material composition 11 of the present invention can be used to manufacture a varistor 10 which provides outstanding electrical properties through the manufacturing steps described below.
  • the present invention further provides a method for manufacturing a varistor whose voltage can be designated as needed.
  • the varistor 10 is constructed of a material composition 11 having a core-shell microstructure which at least comprises a cored-structure 14 wrapped by a shelled-structure 12.
  • the varistor 10 is made by sintering the material composition 11 at a relatively lower temperature.
  • the electrical properties of such varistors 10 can be decided and designated by precisely controlling the size and properties of the grain of cored-structure 14, the thickness and insulation resistance of the insulating layer of the shelled-structure 12, of the interval between two parallel electrodes 21 and the overlap area of the electrodes 21 of the varistors 10.
  • Silicon carbide powders sized between 0.6 ⁇ m and 1.0 ⁇ m are selected and soaked into a transparent organic solution primarily containing ethyl silicate. Trough pH control of the solution, glass containing in the composition can be evenly precipitated on the surface of the silicon carbide powders. Then the powders are dried and sintered at 600°C for 2 hours so that the silicon carbide powders coated with silicate glass can be obtained.
  • the sintered powders are mixed with appropriate binder, dispersant, plasticizer and organic solvent to form an organic paste.
  • the viscosity of the paste is carefully controlled to facilitate the control of the thickness of the green tape to be made.
  • doctor blade casting is conducted with the paste to make a green tape wherein the thickness of the green tape is made to 15 ⁇ 200 ⁇ m.
  • 6 layers of the green tape printed with inner electrodes are stacked in the manner that the inner electrodes alternately appear.
  • the resultant construction is added at the upper and lower end respectively with 5 layers of tape whereon no electrode is printed.
  • the construction is compacted at 70°C and 3000 lb/in 2 (psi) and cut at predetermined positions into green grains.
  • the green grains are further sintered in a sintering furnace at 900°C for 2 hours. Then the sintered grains are coated with silver paste at the appearing end of the inner electrodes and further treated at 800°C for 0.5 hour. Thereby, a multiplayer varistor 10 of Fig. 1 sized 1.0 x 0.5 x 0.5 is obtained.
  • V1mA breakdown voltage
  • ⁇ nonlinear exponent
  • iL leakage current
  • ESD tolerance ESD tolerance
  • Table 1 The measured results are shown in Table 1 and Table 2, wherein Table 1 describes the effect of the amount of the glass on the properties of the varistor 10. According to the results of samples 1 to 5, the larger amount of the glass leads the higher breakdown voltage (V1mA), the higher nonlinear exponent ( ⁇ ) and the lower leakage current (iL) of the varistor 10.
  • Table 2 shows the electrical properties of the varistors 10 made from different thickness of the green tapes sintered at 900°C. It is observed that the breakdown voltages (V1mA) of the varistors 10 are proportioned to the thickness of the green tapes. The thicker the green tape is, the higher breakdown voltage (V1mA) of the resultant varistor 10 has. Table 2 Sample Thickness of the tape ( ⁇ m) V1mA(V) ⁇ iL ( ⁇ A) ESD Tolerence (8KV) 6 20 80.4 11.78 63.5 Pass 7 35 147.2 13.62 57.8 Pass 8 50 235.1 15.08 67.9 Pass 9 70 301.2 14.88 62.3 Pass
  • semi-conductive strontium titanate powders are implemented as the material of the cored-structure of the previous Example 1, while boron glass is used as the material of the shelled-structure.
  • the semi-conductive strontium titanate powders are coated with the boron glass and the chip component fabrication is conducted. Then doctor blade casting is conducted to make a green tape of 50 ⁇ m thickness and the green tape is made into green grains each having two layers of inner electrodes. The construction is sintered at 850°C for 2 hours to obtain a multiple-layered varistor 10.
  • the varistor 10 has electrical properties as shown in Table 3 and can pass the electrostatic discharge immunity test of 8KV.
  • Table 3 Sample Thickness of the tape ( ⁇ m) V1mA(V) ⁇ iL ( ⁇ A) ESD Tolerence (8KV) 10 50 261.8 8.76 2.9 Pass
  • metal nickel powders are implemented as the material of the cored-structure of the previous Example 1, while silicate glass is used as the material of the shelled-structure.
  • the metal nickel powders are coated with the silicate glass and the chip component fabrication is conducted.
  • doctor blade casting is conducted to make a green tape of 30 ⁇ m thickness and the green tape is made into green grains each having two layers of inner electrodes.
  • the construction is sintered at 800°C for 2 hours to obtain a multiple-layered varistor 10.
  • the varistor 10 has electrical properties as shown in Table 4 and can pass the electrostatic discharge immunity test of 8KV.
  • Table 4 Sample Thickness of the tape ( ⁇ m) V1mA(V) ⁇ iL ( ⁇ A) ESD Tolerance (8KV) 11 30 241.8 - 1.22 Pass
  • metal copper powders are implemented as the material of the cored-structure of the previous Example 1, while silicate glass is used as the material of the shelled-structure.
  • the metal copper powders are coated with the silicate glass and the chip component fabrication is conducted.
  • doctor blade casting is conducted to make a green tape of 50 ⁇ m thickness and the green tape is made into green grains each having two layers of inner electrodes.
  • the construction is sintered at 700°C for 2 hours to obtain a multiple-layered varistor 10.
  • the varistor 10 has electrical properties as shown in Table 5 and can pass the electrostatic discharge immunity test of 8KV.
  • Table 5 Sample Thickness of the tape ( ⁇ m) V1mA(V) ⁇ iL ( ⁇ A) ESD Tolerance (8KV) 12 50 548.5 - 0.67 Pass
  • V1mA breakdown voltage
  • Table 6 Sample Thickness of the tape ( ⁇ m) V1mA(V) ⁇ iL ( ⁇ A) ESD Tolerance (8KV) 13 10.0 285.1 17.58 26.8 Pass 14 2.5 254.3 17.24 27.9 Pass 15 0.8 230.6 16.04 28.6 Pass

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thermistors And Varistors (AREA)

Claims (8)

  1. Composition de matériau pulvérisée (11) pour une varistance (10) comprenant :
    un conducteur en métal, un oxyde métallique semi-conducteur ou un matériau semi-conducteur ; et
    un matériau en verre ;
    caractérisé en ce que
    la composition de matériau pulvérisée a une microstructure noyau-enveloppe, un grain formant une structure de noyau (14) étant faite en conducteur en métal, un oxyde métallique semi-conducteur ou un matériau semi-conducteur mentionné et une structure en enveloppe (12) enveloppée autour de la surface du grain de la structure en noyau (14) pour former une couche isolante étant faite en matériau en verre mentionné.
  2. Composition de matériau selon la revendication 1, le conducteur en métal étant un alliage ou une combinaison de deux alliages ou plus ou une combinaison d'alliages de métaux sélectionnés dans le groupe contenant Fe, Al, Ni, Cu, Ag, Au, Pt et Pd.
  3. Composition de matériau selon la revendication 1, le matériau semi-conducteur étant l'un des éléments ou une combinaison de deux éléments ou plus sélectionnés dans le groupe contenant ZnO, SrTiO3, BaTiO3, SiC, TiO2, SnO2, Si et GaAs.
  4. Composition de matériau selon l'une des revendications 1, le matériau en verre étant sélectionné dans le groupe contenant le verre de silicate, le verre à base de bore, le verre en alumine et silice, le verre de phosphate et le verre de plomb.
  5. Procédé pour fabriquer une varistance faite en composition de matériau pulvérisée (11) selon la revendication 1, la varistance (10) étant faite par frittage de la composition de matériau (11) à une température entre 500°C et 1100°C et la tension de rupture de la varistance (10) étant ajustée en contrôlant précisément la taille du grain de la structure en noyau (14) et/ou en contrôlant l'épaisseur ou la résistance d'isolement de la structure en noyau (12) qui forme la couche d'isolation.
  6. Procédé selon la revendication 5 pour fabriquer une varistance en plusieurs couches (10) comprenant :
    a) sélection de compositions de matériaux pulvérisés (11) comme matériau brut, chacune contenant une microstructure noyau-enveloppe, un grain formant une structure de noyau (14) étant faite en matériau conducteur ou semi-conducteur et une structure en enveloppe (12) enveloppée autour de la surface du grain de la structure en noyau (14) pour former une couche isolante étant faite en matériau en verre ;
    b) mélange desdites compositions de matériaux pulvérisés (11) avec un liant approprié, un dispersant, un plastifiant et un solvant organique pour former un matériau en pâte ;
    c) production d'un ruban vert fait en matériau en pâte par moulage par raclage ;
    d) empilage d'un nombre prédéterminé de rubans verts ayant une électrode intérieure (21) imprimée dessus de telle manière que les extrémités des électrodes intérieures (21) apparaissent en alternance ;
    e) frittage des rubans verts empilés à une température entre 600°C et 1100°C,
    f) la tension de rupture de la varistance (10) étant conçue
    à l'étape a) en contrôlant précisément soit la taille de la structure en noyau (14) ou l'épaisseur de la couche en verre de la structure en enveloppe (12) des compositions de matériaux pulvérisées (11) et/ou
    à l'étape b) en contrôlant précisément l'épaisseur de chaque ruban vert à l'intérieur d'une plage entre 15 µm et 200 µm.
  7. Varistance à plusieurs couches (10) produite par le procédé de la revendication 6, un corps céramique fritté (20) construit à partir des compositions de matériaux pulvérisées (11) contenant une quantité de verre supérieure à 20%.
  8. Varistance à plusieurs couches (10) selon la revendication 7, le matériau conducteur étant sélectionné dans le groupe contenant Fe, Al, Ni, Cu, Ag, Au, Pt et Pd et les alliages de ceux-ci et le matériau semi-conducteur étant sélectionné dans le groupe contenant ZnO, SrTiO3, BaTiO3, SiC, TiO2, SnO2, Si et GaAs.
EP07108464.4A 2007-05-18 2007-05-18 Composition de matériau doté d'une microstructure noyau-enveloppe utilisé pour un varistor Not-in-force EP1993108B1 (fr)

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EP07108464.4A EP1993108B1 (fr) 2007-05-18 2007-05-18 Composition de matériau doté d'une microstructure noyau-enveloppe utilisé pour un varistor

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EP07108464.4A EP1993108B1 (fr) 2007-05-18 2007-05-18 Composition de matériau doté d'une microstructure noyau-enveloppe utilisé pour un varistor

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EP1993108A1 EP1993108A1 (fr) 2008-11-19
EP1993108B1 true EP1993108B1 (fr) 2017-03-01

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI409829B (zh) * 2010-09-03 2013-09-21 Sfi Electronics Technology Inc 一種高溫使用的氧化鋅突波吸收器

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Publication number Priority date Publication date Assignee Title
GB1346851A (en) * 1971-05-21 1974-02-13 Matsushita Electric Ind Co Ltd Varistors
CA1206742A (fr) * 1982-12-24 1986-07-02 Hideyuki Kanai Varistor

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