JP2005183593A - Joined type voltage dependent resistor and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a joined type voltage dependent resistor such as a laminated type varistor which is manufactured by using a lamination method and an integrated calcination method and which is small, efficient and reliable; and to provide a manufacturing method of the resistor. <P>SOLUTION: By charging a plurality of kinds of charging materials to the through holes of respectively different ceramic green sheets, the charging materials charged to the through holes are different from material constituting the respective ceramic green sheets, the charging material charged to a prescribed through hole form the plurality of kinds of different ceramic green sheets between prescribed ceramic green sheets, and the plurality of kinds of ceramic green sheets are laminated in a prescribed order to form a laminate. After integrated calcination so as to cover the exposure surface of the charging material (ZnO)13 from the through hole 12, an external electrode 15 is formed at a prescribed position on the surface of the ceramic lamination 11. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a junction-type voltage-dependent resistor and a method for manufacturing the same, and more specifically, a ceramic diode using a semiconductor ceramic or a diode-type varistor having bidirectional characteristics manufactured using a lamination method and an integral firing method. The present invention relates to a junction-type voltage-dependent resistor such as the above and a manufacturing method thereof.

  One of the conventional junction-type voltage-dependent resistors to which the present invention relates is a multilayer voltage nonlinear resistor (multilayer varistor). In recent years, this multilayer voltage nonlinear resistor has been used as a noise protection element in the mobile phone and other communication equipment markets. In these communication devices, as a characteristic necessary for noise protection, a large surge resistance and an ability to suppress a voltage with a low voltage are being demanded. In addition, in response to environmental problems, there is a growing demand for further suppressing current leakage during mounting in order to support low power consumption.

  Further, as the circuit density is increased, a smaller and more excellent device has been required. In addition, with the increase in the number of electronic devices, parts are required to be inexpensive elements.

FIG. 9 shows an example of a conventional varistor (laminated varistor). As shown in FIG. 9, the multilayer varistor 60 is electrically connected to the internal electrode 63 at the end face of the ceramic sintered body 61 in which the ceramic layers 62 mainly composed of ZnO and the internal electrodes 63 are alternately laminated. The external electrode 64 is disposed (for example, Patent Document 1).
However, according to this conventional multilayer varistor, since the varistor characteristics are taken at the grain boundary of the ceramic, the grain size of the sintered body greatly affects the electrical characteristics, and when trying to obtain a low voltage, High precision particle size control is required. However, it is not always easy to actually control the particle size with high accuracy, and a decrease in yield due to voltage variation becomes a problem. Further, in order to achieve miniaturization, more accurate printing technology and lamination technology are required. However, problems such as misalignment occur and problems such as poor service life have occurred.
Further, when trying to reduce the size by stacking, it is necessary to use a noble metal such as Ag or Pt for the internal electrode, which causes a problem of increasing the cost.

Therefore, a method of joining different types of semiconductors and taking stable electrical characteristics at the interface has been considered. One of such devices is a junction-type voltage-dependent resistor using a ceramic potential barrier (for example, Patent Document 2).
As shown in FIG. 10, this junction type voltage-dependent resistor includes a ZnO layer 53, which is mainly composed of ZnO and crystallized during layer formation, on an electrode 52 disposed on a substrate 51, and a ZnO layer. The ZnO layers 53 and the metal oxide layers 54 that are crystallized at the time of forming the layers are alternately formed on the ZnO layers 53 so as to be bonded to each other, and the conductive paths form the bonding surfaces. It is a ZnO varistor provided with an electrode 56 so as to pass through.

This ZnO varistor is characterized in that the metal oxide layer 54 is crystallized when the layer is formed, and the potential barrier 55 is reliably formed, so that non-linearity is improved and thermal stability is improved. In addition, since the heat treatment after forming the metal oxide layer 54 is unnecessary, the ZnO layer 53 and the metal oxide layer 54 can be prevented from cracking. .
Japanese Patent Laid-Open No. 5-226116 Japanese Patent Laid-Open No. 1-200604

By the way, in the case of the junction-type voltage-dependent resistors of Patent Document 1 and Patent Document 2, since the semiconductor material is exposed on the surface, there is a high possibility that the semiconductor material is directly affected by outside air, and surface leakage is likely to occur. There is. In other words, current flows more easily on the surface of the element than on the inside of the element, and there are defects on the element surface. Flowing state is easy to change. In particular, in the case of a semiconductor material that forms a potential barrier, there is a problem that surface leakage is likely to occur on the barrier surface that appears on the surface, because discharge through the atmosphere is likely to occur in addition to thermal current.
In addition, the ZnO layer and the metal oxide layer in the junction voltage-dependent resistor as in Patent Document 2 are both thin film layers formed by sputtering. In order to form such a thin film layer, a highly clean atmosphere and high vacuum are required, and it is very difficult to control defects of ZnO which is a semiconductor. Further, when a voltage is applied to the obtained junction type voltage dependent resistor, there arises a problem that the junction surfaces diffuse to each other. As a result, there is a problem that sufficient energy cannot be withstood and satisfactory surge resistance cannot be obtained.
Conventionally, a junction voltage-dependent resistor that joins dissimilar semiconductors and has stable electrical characteristics at the interface can be easily manufactured in the same way as a multilayer varistor that exhibits characteristics at grain boundaries. There was no resistive resistor.

  The present invention solves the above problems, and is a compact, high-performance, high-reliability, junction-type voltage-dependent resistor such as a multilayer varistor manufactured using a lamination method and an integral firing method, and It is an object to provide a manufacturing method thereof.

In order to solve the above-described problem, a method for manufacturing a junction voltage-dependent resistor according to the present invention (Claim 1) includes:
(a) preparing a plurality of ceramic green sheets having through holes formed at predetermined positions;
(b) filling the through hole of the ceramic green sheet with a filling material different from the material constituting the ceramic green sheet;
(c) laminating ceramic green sheets filled with the filling material in the through holes to form a laminate;
(d) a step of integrally firing the laminate to form a sintered body;
(e) forming a bonding material layer including a material that forms a potential barrier on the bonding surface with the filling material so as to cover the exposed surface of the filling material from the through hole;
(f) forming an external electrode on the surface of the bonding material layer.

Moreover, the manufacturing method of the junction type voltage dependent resistor of the present invention (Claim 2) is as follows.
(a) preparing a plurality of ceramic green sheets having through holes formed at predetermined positions;
(b) filling the through hole of the ceramic green sheet with a filling material different from the material constituting the ceramic green sheet;
(c) Laminating a ceramic green sheet filled with the filling material in the through-hole, and laminating green sheets containing a material that forms a potential barrier on the joint surface with the filling material on both upper and lower sides. Forming a laminate;
(d) a step of integrally firing the laminate to form a sintered body;
(e) forming an external electrode on the surface of the outermost layer made of a green sheet sintered body on both upper and lower surfaces of the laminate.

Moreover, the manufacturing method of the junction type voltage dependent resistor of the present invention (Claim 3) is as follows.
(a) preparing a plurality of ceramic green sheets having through holes formed at predetermined positions;
(b) Filling the through holes of different ceramic green sheets with a plurality of types of filling materials different from the materials constituting each ceramic green sheet, thereby providing a plurality of types of ceramics with different filling materials between predetermined ceramic green sheets. Forming a green sheet;
(c) forming a laminate by laminating a plurality of types of ceramic green sheets formed in (b) in a predetermined order;
(d) a step of integrally firing the laminate to form a sintered body;
(e) forming an external electrode at a predetermined position on the surface of the sintered body so as to cover the exposed surface of the filling material from the through hole.

Moreover, the manufacturing method of the junction type voltage dependent resistor of the present invention (Claim 4) is as follows.
(a) preparing a plurality of ceramic green sheets having through holes formed at predetermined positions;
(b) Filling the through holes of different ceramic green sheets with a plurality of types of filling materials different from the materials constituting each ceramic green sheet, thereby providing a plurality of types of ceramics with different filling materials between predetermined ceramic green sheets. Forming a green sheet;
(c) forming a laminate by laminating a plurality of types of ceramic green sheets formed in (b) in a predetermined order;
(d) a step of integrally firing the laminate to form a sintered body;
(e) forming a bonding material layer including a material that forms the potential barrier on the bonding surface of the same material as the filling material or the filling material so as to cover the exposed surface of the filling material from the through-hole. When,
(f) forming an external electrode on the surface of the bonding material layer.

Moreover, the manufacturing method of the junction type voltage dependent resistor of the present invention (Claim 5) is as follows.
(a) preparing a plurality of ceramic green sheets having through holes formed at predetermined positions;
(b) Filling the through holes of different ceramic green sheets with a plurality of types of filling materials different from the materials constituting each ceramic green sheet, thereby providing a plurality of types of ceramics with different filling materials between predetermined ceramic green sheets. Forming a green sheet;
(c) A plurality of types of ceramic green sheets formed in (b) are stacked in a predetermined order, and potential barriers are formed on the upper and lower surfaces on the same material as the filler material or on the joint surface with the filler material. Laminating green sheets containing the material to be formed to form a laminate,
(d) a step of integrally firing the laminate to form a sintered body;
(e) forming an external electrode on the surface of the outermost layer made of a green sheet sintered body on both upper and lower surfaces of the laminate.

  According to a sixth aspect of the present invention, there is provided a method for manufacturing a junction-type voltage-dependent resistor, wherein the ceramic green sheet becomes an insulator after sintering.

A method for manufacturing a junction type voltage dependent resistor according to claim 7 is the method for manufacturing a junction type voltage dependent resistor according to any one of claims 1, 2, 6.
(a) The filling material filled in the through hole of the ceramic green sheet is a semiconductor ceramic material mainly composed of ZnO, and the bonding material is at least one of Sr and Ba, and of Mn and Co. A rare earth oxide material containing at least one of which a potential barrier is formed at a junction with the filler,
(b) the filling material filled in the through hole of the ceramic green sheet is a rare earth oxide material containing at least one of Sr and Ba and at least one of Mn and Co; It is a semiconductor ceramic material mainly composed of ZnO, and is characterized in that a potential barrier is formed at the junction with the filler material.

  A method for manufacturing a junction voltage dependent resistor according to claim 8 is the method for manufacturing a junction voltage dependent resistor according to any one of claims 3 to 6, wherein the through hole of the ceramic green sheet is filled. The plurality of types of filler materials are: (a) a semiconductor ceramic material mainly composed of ZnO; (b) a rare earth oxide material containing at least one of Sr and Ba and at least one of Mn and Co; However, it is characterized in that a potential barrier is formed at each junction.

Further, the junction voltage dependent resistor of the present invention (claim 9) is:
A ceramic laminate;
A filling material different from the material constituting the ceramic laminate, filled in through-holes provided in the ceramic laminate,
A bonding material sintered body including a material which is disposed so as to cover at least the exposed surface of the filling material from the through-hole and which forms a potential barrier on the bonding surface with the filling material; or the filling material A green sheet sintered body containing a material in which a potential barrier is formed on the bonding surface;
And an external electrode formed on the surface of the bonding material sintered body or the green sheet sintered body.

Further, the junction voltage dependent resistor of the present invention (claim 10) is:
A ceramic laminate;
The through holes provided in the ceramic laminate are filled in a predetermined order in the depth direction, are made of a material different from the material constituting the ceramic laminate, and a potential barrier is formed at the joint surface of each other. Multiple filling materials;
And an external electrode formed so as to cover the surface of the filling material exposed from the through hole.

Moreover, the junction type voltage dependent resistor of the present invention (claim 11) is:
A ceramic laminate;
The through holes provided in the ceramic laminate are filled in a predetermined order in the depth direction, are made of a material different from the material constituting the ceramic laminate, and a potential barrier is formed at the joint surface of each other. Multiple filling materials;
A joint including a material that is disposed so as to cover an exposed surface of the filler material exposed from the through hole of the ceramic laminate, and that has a potential barrier formed on a joint surface with the filler material. A green sheet sintered body including a material sintered body, or a material in which a potential barrier is formed on a joint surface of the same material as the filling material or the filling material;
And an external electrode formed on the surface of the bonding material sintered body or the green sheet sintered body.

The junction voltage dependent resistor according to claim 12 is:
(a) The filling material filled in the through holes of the ceramic laminate is a semiconductor ceramic material mainly composed of ZnO, and the bonding material is at least one of Sr and Ba and Mn and Co. A rare earth oxide material containing at least one of which a potential barrier is formed at a junction with the filler,
(b) the filling material filled in the through holes of the ceramic laminate is a rare earth oxide material containing at least one of Sr and Ba and at least one of Mn and Co; It is a semiconductor ceramic material mainly composed of ZnO, and is characterized in that a potential barrier is formed at the junction with the filler material.

  Further, the junction type voltage dependent resistor according to claim 13 is characterized in that the plurality of kinds of filling materials filled in the through holes of the ceramic laminate are (a) a semiconductor ceramic material mainly composed of ZnO, and (b) A rare earth oxide material containing at least one of Sr and Ba and at least one of Mn and Co, wherein a potential barrier is formed at the junction.

In the manufacturing method of the junction voltage-dependent resistor according to the present invention (Claim 1), the ceramic green sheet is laminated after filling the through hole of the ceramic green sheet with a filling material different from the material constituting the ceramic green sheet. After forming the laminate and firing integrally, a bonding material layer including a material that forms a potential barrier on the bonding surface with the filling material is formed so as to cover the exposed surface of the filling material from the through hole, Since an external electrode is formed on the bonding material layer, a junction-type voltage-dependent resistor manufactured through a process of alternately laminating a plurality of electrode material pastes and ceramic green sheets as shown in FIG. Good electrical characteristics such as diodes and diodes at the bonding interface between the filling material and the bonding material without causing problems such as delamination that may occur in the vessel. Efficient and simple manufacture of diode-type varistors such as diodes and diode-type varistors with high voltage non-linearity, low resistance, and stable characteristics by generating an Ode-type varistor (voltage non-linear resistance) Is possible. In particular, since the through holes are opened and the green sheets filled with the filling material are stacked and sintered, delamination hardly occurs.
In addition, when the bonding material layer is a semiconductor material, an external electrode is formed on the surface thereof, so that a soldering voltage-dependent resistor capable of ensuring solder wettability and allowing a larger current to flow is obtained. be able to. For the external electrode, a method of applying and baking a conductive paste, a method of plating, a method of plating on a baking electrode, or the like can be used, and the specific method is not particularly limited.

Moreover, the manufacturing method of the junction-type voltage-dependent resistor of the present invention (Claim 2) is the method of filling the through hole of the ceramic green sheet with a filling material different from the constituent material of the ceramic green sheet, After laminating, green sheets containing a material that forms a potential barrier on the joint surface with the filler material are laminated on both the upper and lower surfaces to form a laminate, integrally fired, and then exposed to the filler material from the through hole A bonding material layer made of a material that forms a potential barrier is formed on the bonding surface with the filling material so as to cover the surface, and an external electrode is formed on the bonding material layer. Without causing the occurrence, good electrical characteristics such as diodes and diode-type varistors are produced at the bonding interface between the filling material and the bonding material, and the voltage non-linearity is high and low. The junction voltage dependent resistor, such as stable diode or diode type varistor of anti and characteristics it is possible to efficiently manufacture.
In addition, since the external electrode is formed on the surface of the outermost layer made of the green sheet sintered body, a junction-type voltage-dependent resistor with better strength and moisture resistance can be obtained.

  Moreover, the manufacturing method of the junction-type voltage dependent resistor of the present invention (Claim 3) prepares a plurality of ceramic green sheets in which through holes are formed at predetermined positions, and a material constituting each ceramic green sheet; By filling different through-holes in different ceramic green sheets with different types of filler materials, the filler materials form different types of ceramic green sheets between predetermined ceramic green sheets, and the plurality of types of ceramic green sheets After the sheets are laminated in a predetermined order to form a laminated body and integrally fired, external electrodes are formed at predetermined positions on the surface of the sintered body so as to cover the exposed surface of the filling material from the through holes. Therefore, good electrical characteristics at the bonding interface between the filling material and the bonding material without causing problems such as delamination, And cause if diode or diode type varistor example, the voltage nonlinearity high, it is possible to efficiently produce a junction voltage dependent resistor, such as stable diode or diode type varistor having a low resistance and properties. Since the joint portion between the filling material and the joining material, which is a characteristic portion, has a structure located inside the through hole, the characteristic portion is not easily affected by outside air or plating.

  Moreover, the manufacturing method of the junction-type voltage dependent resistor of the present invention (Claim 4) prepares a plurality of ceramic green sheets having through holes formed at predetermined positions, and a material constituting each ceramic green sheet; By filling different through-holes in different ceramic green sheets with different types of filler materials, the filler materials form different types of ceramic green sheets between predetermined ceramic green sheets, and the plurality of types of ceramic green sheets After the sheets are laminated in a predetermined order to form a laminated body and integrally fired, a potential barrier is formed on the joint surface of the same material as the filling material or the filling material so as to cover the exposed surface of the filling material from the through hole. Since a bonding material layer including the material to be formed is formed and an external electrode is formed on the bonding material layer, delamination, etc. A diode with high voltage non-linearity, low resistance, and stable characteristics by causing good electrical characteristics such as diodes and diode-type varistors at the bonding interface between the filling material and the bonding material without causing problems. It is possible to efficiently manufacture a junction type voltage dependent resistor such as a diode type varistor. Since the joint portion between the filling material and the joining material, which is a characteristic portion, has a structure located inside the through hole, the characteristic portion is not easily affected by outside air or plating.

  Moreover, the manufacturing method of the junction-type voltage dependent resistor of the present invention (Claim 5) prepares a plurality of ceramic green sheets in which through holes are formed at predetermined positions, and a material constituting each ceramic green sheet; By filling different through-holes in different ceramic green sheets with different types of filler materials, the filler materials form different types of ceramic green sheets between predetermined ceramic green sheets, and the plurality of types of ceramic green sheets The sheets are laminated in a predetermined order, and a laminate is formed by laminating green sheets containing the same material as the filling material or a material that forms a potential barrier on the joint surface with the filling material on both upper and lower sides to form a laminate. After firing, external electrodes are formed on the surface of the outermost layer consisting of green sheet sintered bodies on the upper and lower surfaces of the laminate. As a result, good electrical characteristics such as diodes and diode-type varistors are generated at the bonding interface between the filling material and the bonding material without causing problems such as delamination, and voltage non-linearity is high and low. It becomes possible to efficiently manufacture a junction-type voltage-dependent resistor such as a diode and a diode-type varistor with stable resistance and characteristics. Since the joint portion between the filling material and the joining material, which is a characteristic portion, has a structure located inside the through hole, the characteristic portion is not easily affected by outside air or plating. Moreover, since the outermost layer covering the through hole is made of a green sheet sintered body, strength and moisture resistance are improved.

Moreover, since the manufacturing method of the junction type voltage dependent resistor of Claim 6 uses what becomes an insulator after sintering as a ceramic green sheet, depending on the kind of filling material, it is influenced by outside air, It is possible to suppress or prevent the occurrence of surface leakage, and it is possible to manufacture a highly reliable junction voltage-dependent resistor.
There are no particular restrictions on the type of insulating material, but it is desirable to use a material that has good adhesion between ZnO or ZnO and a material that forms a potential barrier, such as a mullite composition or a glass composition, and whose shrinkage characteristics are adjusted.
As described above, in the case of the configurations of Patent Document 1 (Japanese Patent Laid-Open No. 5-226116) and Patent Document 2 (Japanese Patent Laid-Open No. 1-200604), the semiconductor material is exposed on the surface, and the influence of the outside air There is a problem that surface leakage is likely to occur. In other words, current flows more easily on the surface of the element than on the inside of the element, and there are defects on the element surface. Flowing state is easy to change. In particular, in the case of a semiconductor material that forms a potential barrier, there is a problem that surface leakage is likely to occur on the barrier surface that appears on the surface, because discharge through the atmosphere is likely to occur in addition to thermal current.
However, as in the method for manufacturing a junction voltage-dependent resistor according to claim 6, by using a ceramic green sheet that becomes an insulator after sintering, it is affected by outside air or surface leakage occurs. The effect that it becomes possible to suppress and prevent this is obtained, which is preferable.

  According to a seventh aspect of the present invention, there is provided a method of manufacturing a junction-type voltage-dependent resistor, wherein (a) a semiconductor ceramic material mainly composed of ZnO is used as a filling material, and at least one of Sr and Ba is used as a bonding material; A rare earth oxide material containing at least one of Mn and Co, wherein a potential barrier is formed at the junction with the filling material, or (b) a filling material of Sr and Ba A rare earth oxide material including at least one and at least one of Mn and Co is used as a bonding material, which is a semiconductor ceramic material mainly composed of ZnO, and forms a potential barrier at the bonding portion with the filling material. Therefore, sintering makes it possible to generate a good voltage nonlinear resistance at the bonding interface between the filler material and the bonding material, and the voltage nonlinearity is high. It is possible to efficiently manufacture a junction-type voltage-dependent resistor (for example, a diode or a diode-type varistor) having low resistance and stable characteristics.

  According to another aspect of the present invention, there is provided a method for manufacturing a junction voltage-dependent resistor comprising: (a) a semiconductor ceramic material mainly composed of ZnO; and (b) at least one of Sr and Ba. , A rare earth oxide material containing at least one of Mn and Co, in which a potential barrier is formed at the junction between them, so that a semiconductor ceramic (n Type semiconductor layer) and a rare earth oxide (p-type or M-type semiconductor layer) junction (pn junction or Mn junction) can produce a good voltage non-linear resistance. Therefore, it is possible to more reliably manufacture a junction voltage-dependent resistor (for example, a diode or a diode-type varistor) having high voltage nonlinearity, low resistance and stable characteristics.

  Further, the junction voltage-dependent resistor of the present invention (Claim 9) is a filling material different from the material constituting the ceramic laminated body, which is filled in the ceramic laminated body and through holes provided in the ceramic laminated body. And a bonding material sintered body including a material which is disposed so as to cover the exposed surface of the filling material and which has a potential barrier formed on the bonding surface with the filling material, or a potential barrier is formed on the bonding surface with the filling material. The structure is equipped with a green sheet sintered body containing the material to be bonded and an external electrode formed on the surface of the bonding material sintered body or the green sheet sintered body, so that problems such as delamination occur. It is possible to obtain good electrical characteristics such as diode characteristics and diode-type varistor characteristics at the bonding interface between the filling material and the bonding material without incurring high voltage nonlinearity, low resistance, and characteristics. It becomes possible to realize the junction voltage dependent resistor, such as boss was a diode or a diode varistor.

  The junction voltage-dependent resistor according to the present invention (Claim 10) includes a ceramic laminate, and through holes provided in the ceramic laminate are filled in a predetermined order in the depth direction. A structure comprising a plurality of filling materials made of a material different from the constituting material and having a potential barrier formed on a joint surface thereof, and an external electrode formed so as to cover the surface of the exposed filling material; Therefore, it is possible to obtain good electrical characteristics such as diodes and diode-type varistors at the bonding interface between the filling material and the bonding material without causing problems such as delamination and voltage non-linearity. It is possible to realize a junction-type voltage-dependent resistor such as a diode or a diode-type varistor having high performance, low resistance, and stable characteristics. Since the joint portion between the filling material and the joining material, which is a characteristic portion, has a structure located inside the through hole, the characteristic portion is not easily affected by outside air or plating.

  The junction voltage-dependent resistor according to the present invention (invention 11) is filled with ceramic laminates and through holes provided in the ceramic laminates in a predetermined order in the depth direction. A plurality of filling materials made of a material different from the constituent materials and having a potential barrier formed on the joint surface with each other, and the same material or filling as the filling material disposed so as to cover the exposed surface of the filling material Bonded material sintered body including a material in which a potential barrier is formed on the bonding surface with the material, or green sheet sintered body including a material in which a potential barrier is formed on the bonding surface with the same material or the filling material as the filling material, and Since it has a structure including an external electrode formed on the surface of the sintered material of the bonding material or green sheet, it does not cause problems such as delamination and is bonded to the filling material. material Good electrical characteristics such as diode characteristics and diode-type varistor characteristics can be obtained at the junction interface, and voltage-dependent resistance such as diodes and diode-type varistors with high voltage nonlinearity, low resistance and stable characteristics Can be realized. Since the joint portion between the filling material and the joining material, which is a characteristic portion, has a structure located inside the through hole, the characteristic portion is not easily affected by outside air or plating.

The junction voltage-dependent resistor according to claim 12 is: (a) the filling material is a semiconductor ceramic material mainly composed of ZnO, and the bonding material is at least one of Sr and Ba, Mn and Co Or a rare earth oxide material containing at least one of them, and a potential barrier is formed at the junction with the filler material,
(b) The filling material is a rare earth oxide material containing at least one of Sr and Ba and at least one of Mn and Co; the bonding material is a semiconductor ceramic material mainly composed of ZnO; Since a potential barrier is formed at the joint with the material, it becomes possible to obtain a good voltage nonlinear resistance at the joint interface between the sintered filler material and the joining material, and the voltage nonlinearity is high and the resistance is low. In addition, a junction-type voltage-dependent resistor (for example, a diode or a diode-type varistor) having stable characteristics can be obtained.

  The junction voltage-dependent resistor according to claim 13 includes: (a) a semiconductor ceramic material mainly composed of ZnO; (b) at least one of Sr and Ba; Since a rare earth oxide material containing at least one of Co and having a potential barrier formed at the junction is used, a semiconductor ceramic mainly composed of ZnO (n-type semiconductor layer) And a good voltage non-linear resistance can be generated at the junction (pn junction or Mn junction) of the rare earth oxide (p-type or M-type semiconductor layer). It is possible to reliably obtain a junction-type voltage-dependent resistor (for example, a diode or a diode-type varistor) having high performance, low resistance, and stable characteristics.

  The features of the present invention will be described in more detail below with reference to examples of the present invention.

(1) Production of ceramic green sheet (insulating sheet) 90% by weight of mullite powder having a diameter of 1 μm and 10% by weight of alkali glass near a softening point of 1100 ° C. were weighed and mixed and ground by a ball mill, and then dehydrated and dried.
Ethanol, toluene and a dispersing agent were added to the raw material and dispersed, and then a binder and a plasticizer were added to form a slurry.
Then, using this slurry, a ceramic green sheet having a thickness of 50 μm was produced by a doctor blade method.
Then, as shown in FIG. 1, a through hole 2 having a diameter of 100 μm was formed in the ceramic green sheet 1 by a laser processing method.
As a method for forming the through-hole 2, various methods such as punching (drilling with a mold) and drilling with a jet water flow can be used in addition to the laser processing method.
In addition to the mullite composition (Zn ₂ TiO ₄ ) and glass composition as described above, the ceramic material (insulating material) constituting the ceramic green sheet includes various materials such as Zn ₂ MuO ₄ and SrWO. It is possible to use these materials.

(2) Production of ZnO paste and ZnO sheet ZnO was heat treated at 1000 ° C., pulverized to 1 μm or less with a ball mill, dehydrated and dried, and then made into a paste by adding a solvent and varnish to prepare a ZnO paste.
In addition, after heat-treating ZnO at 1000 ° C., it was pulverized to 1 μm or less with a ball mill, dehydrated and dried ZnO raw material was dispersed by adding ethanol, toluene and a dispersing agent, and a binder and a plasticizer were added to form a slurry. A 50 μm thick ZnO green sheet sheet (ZnO sheet) was prepared by the doctor blade method.
Incidentally, as in the case of the first embodiment, in the case of using ZnO as the semiconductor material, as the ceramic material for the ceramic green sheet (insulating material), the like _{SrWO 4, Zn 2 TiO 4,} Zn 2 SiO 4 It is desirable.

(3) Preparation of a material paste that forms a potential barrier with ZnO and a green sheet using the material La ₂ O ₃ , SrCO ₃ , and Mn ₃ O ₄ are La ₂ O ₃ : 0.35 mol SrCO ₃ : 0. 30 mol Mn ₃ O ₄ : Weighed at a ratio of 1.00 mol and wet mixed with a ball mill. And after evaporating and drying the mixture, it heat-processed at 1000 degreeC and made it react temporarily.
Then, the obtained temporary reaction product was once pulverized to 1 μm or less with a ball mill, and a solvent and varnish were added to form a paste.
In addition, ethanol, toluene, and a dispersing agent are added to a raw material obtained by pulverizing the temporary reaction product to 1 μm or less with a ball mill, and then a binder and a plasticizer are added to form a slurry. A green sheet was produced.
Hereinafter, a material containing La ₂ O ₃ , SrCO ₃ and Mn ₃ O ₄ is abbreviated as “LSMO”, a paste prepared using LSMO is a LSMO paste, and a green sheet prepared using LSMO It is called LSMO green sheet.

(4) Filling and drying of ZnO paste In the through hole 2 of the ceramic green sheet (insulating sheet) 1 prepared in the above (1), the ZnO paste 3 prepared in the above (2) is screen-printed as shown in FIG. It was filled by the method and dried.

(5) Filling and drying LSMO paste The LSMO paste 4 (FIG. 2) prepared in (3) above is passed through the through hole 2 of the ceramic green sheet (insulating sheet) 1 prepared in (1) above. In the same manner as in the above, it was filled by screen printing and dried.
In the present invention, it is possible to use a semiconductor material other than ZnO and LSMO as described above, an electrode material, a metal oxide, and the like as the filling material. For example, BaTiO ₃ , SrTiO ₃ , NiO or the like can be filled.
Further, as a method for filling the through hole with the filling material, various methods such as a method using a dispenser, a method using a dispenser, and a method of cutting after embedding a tube can be used as well. .

(6) Lamination Then, the ZnO-filled sheet and the LSMO-filled sheet prepared in the above (4) and (5) are laminated in a predetermined order, and are pressure-bonded at a pressure of 1.96 × 10 ⁹ Pa. Crimping block) was produced.

(7) Cutting the Mother Laminated Body The mother laminated body (crimp block) 6 produced in (6) above is cut with a dicer perpendicular to the laminated surface, for example, along the cutting line L in FIG. A 0.5 mm × 0.5 mm firing precursor (unfired junction-type voltage-dependent resistor element (hereinafter also simply referred to as “element”) was produced.

(8) Firing The fired precursor (unfired element) prepared in (7) above was degreased at 600 ° C. and then fired at 1300 ° C. for 3 hours to obtain a sintered body (ceramic laminate).

(9) Formation of external electrode By forming the external electrode 15 on the sintered body (ceramic laminate) formed in the above (8), the junction type voltage dependency as shown in FIGS. A resistor was obtained.
The external electrode can be formed by various methods such as a method of forming a plated metal film, a method of applying and baking a conductive paste, and a dry thin film forming method.

Note that a junction-type voltage-dependent resistor is also manufactured as follows. That is, as shown in FIG. 3, a plurality of ceramic green sheets 1 filled with ZnO paste 3 in the through-holes 2 are laminated, and LSMO green sheets 5 are laminated on both upper and lower surfaces thereof to obtain 1.96 × 10 ⁹ Pa. The mother laminate (crimp block) 6 is formed by press-bonding with the pressure. Then, this mother laminate (crimp block) 6 is cut and fired as in (7) and (8) above, and then external electrodes are formed as in (9) above. In this case, as shown in FIG. 5 (c), the ceramic laminate 11 and the filling made of a material different from the material constituting the ceramic laminate 11 filled in the through holes 12 provided in the ceramic laminate 11 are used. Green sheet sintering in which a potential barrier is formed on the joint surface between the material (ZnO) 13 and the filler material (ZnO) 13 disposed so as to cover the exposed surface of the filler material (ZnO) 13 from the through hole. A junction-type voltage-dependent resistor including the body (LSMO green sheet sintered body) 14a and the external electrode 15 formed on the surface of the LSMO green sheet sheet sintered body 14a is obtained.
In addition, various junction-type voltage-dependent resistors can be manufactured by appropriately selecting and combining ceramic green sheets, filling materials, and constituent materials of green sheets that form a potential barrier on the joint surface with the filling materials. Is possible.

  Hereinafter, the configuration of the junction voltage-dependent resistor shown in FIGS. 5A to 5E and the manufacturing method thereof will be described. 5 (a) to 5 (e) show the configuration of each junction type voltage-dependent resistor when the stacking direction of the mother laminate (crimp block) 6 in FIG. 3 is horizontal. It is sectional drawing.

The junction voltage-dependent resistors (samples A1 and B1 in Table 1) shown in FIGS. 5A and 5B have two kinds of filling materials (ZnO13) alternately filled in the through holes 12 of the ceramic laminate 11. And LSMO 14) and a green sheet sintered body (ZnO green sheet firing) disposed on both end faces of the ceramic laminate 11 so as to be electrically connected to the ZnO 13 exposed from the openings on both ends of the through holes 12 of the ceramic laminate 11. (Consolidated) 13a and an external electrode 15 disposed on the surface of the ZnO green sheet sintered body 13a.
The junction-type voltage-dependent resistor includes, as a filling material, a ceramic green sheet in which a through hole is filled with ZnO paste and a ceramic green sheet in which a through hole is filled with LSMO paste in a predetermined order. A ZnO green sheet is laminated on the upper and lower sides, pressure-bonded, cut, fired, and then manufactured by forming external electrodes on the surface of the ZnO green sheet sintered body.

Further, the junction-type voltage-dependent resistor (sample C1 in Table 1) of FIG. 5C includes a filling material (ZnO 13) filled in the through holes 12 of the ceramic laminate 11, and the through holes of the ceramic laminate 11. 12 LSMO green sheet sintered body 14 a disposed on both end faces of the ceramic laminate 11 and the surfaces of the LSMO green sheet sintered body 14 a so as to be electrically connected to the ZnO 13 exposed from the openings on both end sides of 12. The external electrode 15 is provided.
This junction-type voltage-dependent resistor is formed by laminating ceramic green sheets filled with ZnO paste in through-holes as a filling material, and further laminating and pressing LSMO green sheets on the top and bottom, cutting, firing Then, an external electrode is formed on the surface of the LSMO green sheet sintered body.

Further, the junction voltage-dependent resistor (sample D1 in Table 1) in FIG. 5D includes the LSMO 14 of the filling material filled in one side (left side) of the through hole 12 of the ceramic laminate 11, and the other side. The ZnO 13 filled on the right side and the LSMO 14 exposed from one opening of the through-hole 12 of the ceramic laminate 11 are electrically connected to the ZnO green sheet disposed on one end face of the ceramic laminate 11. The LSMO green sheet sintered body 14a, the ZnO green sheet sintered body 13a, and the LSMO green disposed on the other end surface of the ceramic laminate 11 so as to be electrically connected to the bonded body 13a and the ZnO 13 exposed from the other opening. It has the structure provided with the external electrode 15 arrange | positioned on the surface of the sheet sintered compact 14a.
The junction-type voltage-dependent resistor includes, as a filling material, a ceramic green sheet in which a through hole is filled with ZnO paste and a ceramic green sheet in which a through hole is filled with LSMO paste in a predetermined order. A ZnO green sheet is laminated on one of the upper and lower sides, and an LSMO green sheet is laminated on the other, pressure-bonded, cut and fired, and then external electrodes are formed on the surfaces of the ZnO green sheet sintered body and the LSMO green sheet sintered body. It is manufactured by forming.

In addition, the junction-type voltage-dependent resistor (sample E1 in Table 1) in FIG. 5 (e) includes a filling material ZnO 13 filled in one side (left side) of the through hole 12 of the ceramic laminate 11, and the other side. The LSMO 14 filled in (right side) and the ZnO green sheet fired on one end face of the ceramic laminate 11 so as to be electrically connected to the ZnO 13 exposed from one opening of the through hole 12 of the ceramic laminate 11. The LSMO green sheet sintered body 14a, the ZnO green sheet sintered body 13a, and the LSMO green disposed on the other end face of the ceramic laminate 11 so as to be electrically connected to the ligated body 13a and the LSMO 14 exposed from the other opening. It has the structure provided with the external electrode 15 arrange | positioned on the surface of the sheet sintered compact 14a.
In addition, in the junction type voltage dependent resistor of FIGS. 5 (a) to 5 (e) manufactured by the method of Example 1, the junction type voltage dependent resistor of FIG. 5 (e) uses a semiconductor ceramic. 5 is a diode-type varistor having a bidirectional characteristic.
The junction-type voltage-dependent resistor includes, as a filling material, a ceramic green sheet in which a through hole is filled with ZnO paste and a ceramic green sheet in which a through hole is filled with LSMO paste in a predetermined order. A LSMO green sheet is laminated on one of the upper and lower sides, and a ZnO green sheet is laminated on the other, pressure-bonded, cut and fired, and then external electrodes are formed on the surfaces of the ZnO green sheet sintered body and the LSMO green sheet sintered body. It is manufactured by forming.
Note that the combination of the materials of the junction voltage-dependent resistor (relationship between LSMO and ZnO) shown in FIGS. 5A to 5E can be reversed.

In this Example 2,
(1) Fabrication of ceramic green sheets (insulating sheets)
(2) Preparation of ZnO paste
(3) Preparation of a material paste that forms a potential barrier with ZnO
(4) Filling and drying ZnO paste
(5) Since each step of filling and drying the LSMO paste is the same as in the case of Example 1, the description of Example 1 is used, the description is omitted, and the subsequent steps are described.
However, in Example 2, a green sheet using a ZnO sheet and a material that forms a potential barrier with ZnO was not manufactured.

(6) Lamination The ZnO-filled sheet and LSMO-filled sheet prepared in the above (4) and (5) are laminated in a predetermined order, and are pressure-bonded at a pressure of 1.96 × 10 ⁹ Pa. ) Was produced.

(7) Cutting the Mother Laminated Body The mother laminated body (crimp block) 6 produced in (6) above is cut with a dicer perpendicular to the laminated surface along the cutting line L in FIG. A 0.5 mm × 0.5 mm firing precursor (unfired element) was prepared.

(8) Firing The fired precursor (unfired element) prepared in (7) above was degreased at 600 ° C. and then fired at 1300 ° C. for 3 hours to obtain a sintered body (ceramic laminate).

(9) Formation of bonding material layer ZnO paste and LSMO paste were applied to both ends of the sintered body (ceramic laminate) prepared in (8) so as to cover the exposed surface of the filler exposed from the through hole. Then, a bonding material layer was formed and baked at 1200 ° C. for 30 minutes to obtain a ceramic laminate including bonding material sintered bodies on both end surfaces.
In addition, some ceramic laminated bodies were left as they were without forming a bonding material sintered body.

(10) Formation of External Electrode By forming the external electrode 15 on the ceramic sintered body provided with the bonding material sintered body formed in the above (9), bonding as shown in FIGS. A type voltage dependent resistor was obtained.

Note that a junction-type voltage-dependent resistor is also manufactured as follows. That is, as shown in FIG. 6, a plurality of ceramic green sheets 1 filled with ZnO paste 3 are stacked in the through-holes 2 and pressed with a pressure of 1.96 × 10 ⁹ Pa to obtain a mother laminate (crimping block). ) 6 is formed. Then, this mother laminate (crimp block) 6 is cut and fired as in (7) and (8) above, and then the filling material (ZnO) 13 from the through hole 2 as in (9) above. A bonding material layer (LSMO layer) 14b made of LSMO in which a potential barrier is formed on the bonding surface with the filling material is formed so as to cover the exposed surface. Then, by forming external electrodes on the surface of the LSMO layer (bonding material layer) 14b as shown in (10) above, the ceramic laminate 11 and the ceramic laminate 11 are formed as shown in FIG. Covering the exposed surface of the filling material (ZnO) 13 made of a material different from the material constituting the ceramic laminate 11 and filled in the provided through-hole 12 and the filling material (ZnO) 13 from the through-hole. A junction-type voltage including an LSMO layer (bonding material sintered body) 14b in which a potential barrier is formed on a joint surface with a filler material (ZnO) 13 and an external electrode 15 formed on the surface thereof. A dependent resistor is obtained.
In addition, various junction type voltage dependent resistors can be manufactured by appropriately selecting and combining ceramic green sheets, filling materials, bonding materials, and the like.

  Hereinafter, the configuration of the junction type voltage dependent resistor shown in FIGS. 8A to 8F and the manufacturing method thereof will be described. 8A to 8F show the configuration of each junction-type voltage-dependent resistor when the mother laminate (crimp block) 6 shown in FIG. 6 has a horizontal orientation. It is sectional drawing.

Note that the junction voltage-dependent resistors (samples A2 and B2 in Table 2) shown in FIGS. 8A and 8B have two types of filling materials alternately filled in the through-holes 12 of the ceramic laminate 11. (ZnO 13 and LSMO 14) and ZnO layers (bonded material sintered bodies) disposed on both end surfaces of the ceramic laminate 11 so as to be electrically connected to the ZnO 13 exposed from the openings on both ends of the through holes 12 of the ceramic laminate 11 ) 13b and an external electrode 15 disposed on the surface of the ZnO layer (bonding material sintered body) 13b.
This junction voltage-dependent resistor is formed by laminating a ceramic green sheet having a through hole filled with ZnO paste and a ceramic green sheet having a through hole filled with LSMO paste in a predetermined order as a filling material. After cutting and firing, a bonding material layer is formed by applying a ZnO paste so as to cover the exposed surface of the filling material (ZnO) exposed from the through-holes, and sintered, and then sintered. It is manufactured by forming an external electrode on the surface of the bonded body.

Further, the junction-type voltage-dependent resistor (sample C2 in Table 2) of FIG. 8C includes a filling material (ZnO 13) filled in the through holes 12 of the ceramic laminate 11, and the through holes of the ceramic laminate 11. LSMO layers (bonding material sintered bodies) 14b and LSMO layers (bonding material sintered bodies) 14b disposed on both end faces of the ceramic laminate 11 so as to be electrically connected to the ZnO 13 exposed from the openings on both ends of the plate 12. And an external electrode 15 disposed on the surface of the substrate.
And this junction type voltage dependence resistor laminates the ceramic green sheet which filled the through hole with the ZnO paste as a filling material, cuts, baked, and then fills the filling material (ZnO) exposed from the through hole. The LSMO paste is applied so as to cover the exposed surface, a bonding material layer is formed and sintered, and then an external electrode is formed on the surface of the bonding material sintered body.

Further, the junction type voltage dependent resistor (sample D2 in Table 2) of FIG. 8D includes the LSMO 14 of the filling material filled on one side (left side) of the through hole 12 of the ceramic laminate 11, and the other side. A ZnO layer (bonding) disposed on one end surface of the ceramic laminate 11 so as to be electrically connected to the LSMO 14 exposed from one opening of the through hole 12 of the ceramic laminate 11 and the ZnO 13 filled in (right side). Material sintered body) 13b and LSMO layer (bonding material sintered body) 14b disposed on the other end face of the ceramic laminate 11 so as to be electrically connected to ZnO 13 exposed from the other opening, and bonding material sintering It has a configuration provided with external electrodes 15 disposed on the surfaces of the bodies 13b and 14b.
This junction type voltage dependent resistor is formed by laminating a ceramic green sheet having a through hole filled with ZnO paste and a ceramic green sheet having a through hole filled with LSMO paste in a predetermined order as a filling material. Then, after firing, a ZnO paste is applied so as to cover the exposed surface of LSMO exposed from one opening, and an LSMO paste is applied so as to cover the exposed surface of ZnO exposed in the other opening. After the bonding material layer is formed and sintered, an external electrode is formed on the surface of the bonding material sintered body.

Further, the junction-type voltage-dependent resistor (sample E2 in Table 2) of FIG. 8 (e) includes a filling material ZnO 13 filled in one side (left side) of the through hole 12 of the ceramic laminate 11, and the other side. ZnO disposed on one end face of the ceramic laminate 11 so as to be electrically connected to the exposed surface of the ZnO 13 exposed from one opening of the LSMO 14 filled in (right side) and the through hole 12 of the ceramic laminate 11. A LSMO layer (bonding material sintered body) 14b disposed on the other end face of the ceramic laminate 11 so as to be electrically connected to the layer (bonding material sintered body) 13b and the LSMO 14 exposed from the other opening; It has a configuration including a layer (sintered bonding material) 13 b and an external electrode 15 disposed on the surface of the LSMO layer (bonding material sintered body) 14 b.
In addition, in the junction type voltage dependent resistor of FIGS. 8A to 8F manufactured by the method of Example 2, the junction type voltage dependent resistor of FIG. 8E uses a semiconductor ceramic. 8 is a diode type varistor having a bidirectional characteristic.
The junction voltage-dependent resistor is formed by laminating a ceramic green sheet in which a through hole is filled with ZnO paste and a ceramic green sheet in which a through hole is filled with LSMO paste in a predetermined order, cutting and firing. After that, the ZnO paste is applied so as to cover the exposed surface of ZnO exposed from one opening, and the bonding material layer is formed by applying the LSMO paste so as to cover the exposed surface of LSMO exposed in the other opening. After forming and sintering, the external electrode is formed on the surface of the bonding material sintered body.

Further, the junction type voltage dependent resistor (sample F2 in Table 2) of FIG. 8 (f) includes ZnO 13 disposed in the center of the through hole 12 of the ceramic laminate 11, and LSMOs 14 disposed on both sides thereof. In addition, external electrodes 15 are disposed on both end faces of the ceramic laminate 11 so as to be electrically connected to the LSMO 14 exposed from the openings on both ends of the through holes 12 of the ceramic laminate 11.
The junction voltage-dependent resistor is formed by laminating a ceramic green sheet in which a through hole is filled with ZnO paste and a ceramic green sheet in which a through hole is filled with LSMO paste in a predetermined order, cutting and firing. After that, the external electrode is formed by applying and baking a metal paste for the external electrode on both end surfaces of the ceramic laminate so as to cover the exposed surface of the filler material (LSMO) exposed from the through hole. The
Note that the combination of the materials of the junction voltage-dependent resistor (relationship between LSMO and ZnO) shown in FIGS. 5A to 5E can be reversed.
As a conventional technique, a multilayer varistor (L = 1.6 mm, W = 0.8 mm, T = 0.8 mm) described in Patent Document 1 shown in FIG. 9 was manufactured.

[Evaluation of characteristics]
The following characteristics were examined for each sample produced in Example 1 and Example 2 and the conventional example.
(1) Breakdown voltage: V _1mA
(2) Voltage nonlinear coefficient: α
(3) Capacitance (1MHz)
(4) Ratio of the voltage across the sample when a DC current of 1 μA is applied to the breakdown voltage V _{1 mA} : V _{1 μA} / V _{1 mA}
(5) Limiting voltage ratio: V _1A / V _1mA
(6) Varistor voltage change (surge change)

Breakdown voltage: V _{1 mA} is a value obtained by measuring the voltage across the sample when a DC current of 1 _mA was passed.
Voltage non-linear coefficient: α is a value obtained by the following equation from the voltage across the sample and a breakdown voltage when a DC current of 0.1 mA is passed.
α = log (I _1mA / I _0.1mA )) / log (V _1mA / V _0.1mA )
The capacitance is a value obtained by measuring the capacitance at 1 MHz with an LCR meter.
V _{1 μA} / V _{1 mA} is obtained by measuring the voltage across the sample when a DC current of ₁ μA is passed and determining the ratio (V _{1 μA} / V _{1 mA} ) to the breakdown voltage V _{1 mA} .
Limiting voltage ratio: V _1A / V _1mA is a triangular waveform of 8 × 20 μs, and a peak voltage when the voltage across the sample is measured by applying a current surge having a current peak of 1 A to the sample: V _1A The ratio of the breakdown voltage V1 _mA is V _1A / V _{1 mA} .
The change (surge change) of the varistor voltage is a value of change (surge change) of the varistor voltage, which was examined by applying a current surge having a triangular waveform of 8 × 20 μsec and a current peak of 30 A to the sample.
Tables 1 and 2 show the measurement results of each characteristic.

  In both Example 1 and Example 2, good effects were obtained with respect to each characteristic. When Example 1 and Example 2 were compared, Example 1 was relatively changed in varistor voltage (surge). (Change) is small, and it is understood that it is strong against surge. This is considered to be because the derived green sheet sintered body is sufficiently sintered. However, as shown in Tables 1 and 2, both Example 1 and Example 2 were compared with a conventional junction voltage-dependent resistor (multilayer varistor (ZnO varistor) having a structure as shown in FIG. 9). It has been confirmed that the electrical characteristics are improved.

  The junction voltage-dependent resistors (ceramic diodes, diode-type varistors) of Examples 1 and 2 are ZnO, a material that forms a potential barrier with ZnO (LSMO in Examples 1 and 2), and an insulating material (ceramic) ), And an external electrode (plated metal or the like), and the main electrical characteristics are determined by characteristics obtained from ZnO and the LSMO junction that forms a potential barrier with ZnO. For this reason, it is possible to obtain a junction-type voltage-dependent resistor that has a small breakdown voltage variation and is easy to design.

  In addition, in the case where the joint portion between ZnO and LSMO is in the through hole, since the element portion is covered with the integrally sintered insulating layer, the surface current can be suppressed and the leakage current can be reduced. It becomes possible, and it becomes possible to improve moisture resistance. In particular, when the outermost layer of the layers covering the through holes is a green sheet sintered body, the effect is enhanced.

Furthermore, when the ZnO and LSMO joint is in the through-hole of the ceramic laminate, the characteristics are less likely to be lost due to the penetration of the plating solution. An external electrode can be formed, and a highly reliable junction voltage-dependent resistor can be provided.
Further, when the outermost layer covering the through-hole is ZnO, the plating easily grows on the ZnO, so that direct plating can be performed, and the external electrode can be formed only with the plated metal film. It becomes possible. When the external electrode is formed of a plated metal film, it is particularly effective to use a Zn plated film so that ohmic contact between the external electrode and ZnO can be easily secured.

In addition, according to the present invention, it is possible to manufacture a low-capacitance, low-voltage junction type voltage-dependent resistor, and it is possible to cope with an increase in signal speed. Further, by selecting a material having a low dielectric constant for the insulator, it is possible to reduce the stray capacitance generated between the electrode terminals.
Furthermore, since the junction-type voltage-dependent resistor of the present invention can be manufactured by a relatively simple process, the product cost can be reduced.

  In the above embodiments, ceramic diodes and diode-type varistors having bidirectional characteristics have been described as examples. However, the invention of the junction voltage-dependent resistor of the present invention and the manufacturing method thereof is not limited thereto. Rather, it can be applied to an electronic component in which a potential barrier is formed and characteristics are produced by joining ceramic materials.

  The present invention is not limited to the above-described embodiment in other points, and various applications and modifications can be made within the scope of the invention.

According to the present invention, as described above, it is possible to generate a good voltage non-linear resistance at the bonding interface between the filling material and the bonding material without causing the occurrence of delamination or the like. Therefore, it is possible to obtain a junction voltage-dependent resistor such as a diode or a diode-type varistor having high performance, low resistance, and stable characteristics.
Therefore, the present invention can be widely used in industrial fields such as diodes, diode-type varistors, and composite electronic parts thereof.

In one embodiment (Example 1) of this invention, it is a figure which shows the state which formed the through-hole in the ceramic green sheet. In Example 1, it is a figure which shows the state which filled the through-hole of the ceramic green sheet with the filling material. In Example 1, it is a figure which shows the method of laminating | stacking a ceramic green sheet etc. and forming a non-baking laminated body (crimp block). It is a figure explaining the method of cutting the unbaked laminated body formed in Example 1. FIG. (a)-(e) is sectional drawing which shows the structure of the electronic component manufactured in Example 1. FIG. In other embodiment (Example 2) of this invention, it is a figure which shows the method of forming a laminated body (crimp block) by laminating | stacking several ceramic green sheets with which the through-hole was filled with the filling material (ZnO paste). . It is a figure explaining the method of cutting the unbaked laminated body formed in Example 2. FIG. (a)-(f) is sectional drawing which shows the structure of the electronic component manufactured in Example 2. FIG. It is sectional drawing which shows the structure of the conventional multilayer varistor (patent document 1). It is a figure which shows the structure of the conventional (patent document 2) ZnO varistor.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Ceramic green sheet 2 Through hole of ceramic green sheet 3 ZnO paste 4 LSMO paste 5 LSMO green sheet 6 Mother laminated body (crimp block)
DESCRIPTION OF SYMBOLS 11 Ceramic laminated body 12 Through-hole of ceramic laminated body 13 ZnO
13a Green sheet sintered body (ZnO green sheet sintered body)
13b ZnO layer (bonded material sintered body)
14 LSMO
14a Green sheet sintered body (LSMO green sheet sintered body)
14b LSMO layer (bonded material sintered body)
15 External electrode L Cutting line

Claims (13)

(a) preparing a plurality of ceramic green sheets having through holes formed at predetermined positions;
(b) filling the through hole of the ceramic green sheet with a filling material different from the material constituting the ceramic green sheet;
(c) laminating ceramic green sheets filled with the filling material in the through holes to form a laminate;
(d) a step of integrally firing the laminate to form a sintered body;
(e) forming a bonding material layer including a material that forms a potential barrier on the bonding surface with the filling material so as to cover the exposed surface of the filling material from the through hole;
and (f) forming an external electrode on the surface of the bonding material layer. A method for manufacturing a junction-type voltage dependent resistor. (a) preparing a plurality of ceramic green sheets having through holes formed at predetermined positions;
(b) filling the through hole of the ceramic green sheet with a filling material different from the material constituting the ceramic green sheet;
(c) Laminating a ceramic green sheet filled with the filling material in the through-hole, and laminating green sheets containing a material that forms a potential barrier on the joint surface with the filling material on both upper and lower sides. Forming a laminate;
(d) a step of integrally firing the laminate to form a sintered body;
(e) forming an external electrode on the surface of the outermost layer made of a green sheet sintered body on both the upper and lower surfaces of the laminate, and a method for producing a junction-type voltage-dependent resistor. (a) preparing a plurality of ceramic green sheets having through holes formed at predetermined positions;
(b) Filling the through holes of different ceramic green sheets with a plurality of types of filling materials different from the materials constituting each ceramic green sheet, thereby providing a plurality of types of ceramics with different filling materials between predetermined ceramic green sheets. Preparing a green sheet;
(c) forming a laminate by laminating a plurality of types of ceramic green sheets formed in (b) in a predetermined order;
(d) a step of integrally firing the laminate to form a sintered body;
and (e) forming an external electrode at a predetermined position on the surface of the sintered body so as to cover the exposed surface of the filling material from the through hole. Manufacturing method of resistors. (a) preparing a plurality of ceramic green sheets having through holes formed at predetermined positions;
(b) Filling the through holes of different ceramic green sheets with a plurality of types of filling materials different from the materials constituting each ceramic green sheet, thereby providing a plurality of types of ceramics with different filling materials between predetermined ceramic green sheets. Preparing a green sheet;
(c) forming a laminate by laminating a plurality of types of ceramic green sheets formed in (b) in a predetermined order;
(d) a step of integrally firing the laminate to form a sintered body;
(e) forming a bonding material layer including a material that forms the potential barrier on the bonding surface of the same material as the filling material or the filling material so as to cover the exposed surface of the filling material from the through-hole. When,
and (f) forming an external electrode on the surface of the bonding material layer. A method for manufacturing a junction-type voltage dependent resistor. (a) preparing a plurality of ceramic green sheets having through holes formed at predetermined positions;
(b) Filling the through holes of different ceramic green sheets with a plurality of types of filling materials different from the materials constituting each ceramic green sheet, thereby providing a plurality of types of ceramics with different filling materials between predetermined ceramic green sheets. Preparing a green sheet;
(c) A plurality of types of ceramic green sheets formed in (b) are stacked in a predetermined order, and potential barriers are formed on the upper and lower surfaces on the same material as the filler material or on the joint surface with the filler material. Laminating green sheets containing the material to be formed to form a laminate,
(d) a step of integrally firing the laminate to form a sintered body;
(e) forming an external electrode on the surface of the outermost layer made of a green sheet sintered body on both the upper and lower surfaces of the laminate, and a method for producing a junction-type voltage-dependent resistor.   6. The method of manufacturing a junction type voltage dependent resistor according to claim 1, wherein the ceramic green sheet becomes an insulator after sintering. (a) The filling material filled in the through hole of the ceramic green sheet is a semiconductor ceramic material mainly composed of ZnO, and the bonding material is at least one of Sr and Ba, and of Mn and Co. A rare earth oxide material containing at least one of which a potential barrier is formed at a junction with the filler,
(b) the filling material filled in the through hole of the ceramic green sheet is a rare earth oxide material containing at least one of Sr and Ba and at least one of Mn and Co; The junction-type voltage according to claim 1, wherein the junction-type voltage is a semiconductor ceramic material mainly composed of ZnO, and a potential barrier is formed at a junction with the filling material. Dependent resistor manufacturing method.   The plurality of types of filling materials filled in the through holes of the ceramic green sheet are (a) a semiconductor ceramic material mainly composed of ZnO, (b) at least one of Sr and Ba, and at least of Mn and Co. 7. A junction-type voltage-dependent resistor according to claim 3, wherein a potential barrier is formed at the junction between the two rare-earth oxide materials. Manufacturing method. A ceramic laminate;
A filling material different from the material constituting the ceramic laminate, filled in through-holes provided in the ceramic laminate,
A bonding material sintered body including a material which is disposed so as to cover at least the exposed surface of the filling material from the through-hole and which forms a potential barrier on the bonding surface with the filling material; or the filling material A green sheet sintered body containing a material in which a potential barrier is formed on the bonding surface;
An external electrode formed on the surface of the bonding material sintered body or the green sheet sintered body. A ceramic laminate;
The through holes provided in the ceramic laminate are filled in a predetermined order in the depth direction, are made of a material different from the material constituting the ceramic laminate, and a potential barrier is formed at the joint surface of each other. Multiple filling materials;
An external electrode formed so as to cover the surface of the filling material exposed from the through hole. A ceramic laminate;
The through holes provided in the ceramic laminate are filled in a predetermined order in the depth direction, are made of a material different from the material constituting the ceramic laminate, and a potential barrier is formed at the joint surface of each other. Multiple filling materials;
A joint including a material that is disposed so as to cover an exposed surface of the filler material exposed from the through hole of the ceramic laminate, and that has a potential barrier formed on a joint surface with the filler material. A green sheet sintered body including a material sintered body, or a material in which a potential barrier is formed on a joint surface of the same material as the filling material or the filling material;
An external electrode formed on the surface of the bonding material sintered body or the green sheet sintered body. (a) The filling material filled in the through holes of the ceramic laminate is a semiconductor ceramic material mainly composed of ZnO, and the bonding material is at least one of Sr and Ba and Mn and Co. A rare earth oxide material containing at least one of which a potential barrier is formed at a junction with the filler,
(b) the filling material filled in the through holes of the ceramic laminate is a rare earth oxide material containing at least one of Sr and Ba and at least one of Mn and Co; The junction-type voltage-dependent resistor according to claim 9, wherein the junction-type voltage-dependent resistor is a semiconductor ceramic material mainly composed of ZnO, and a potential barrier is formed at a junction with the filling material.   The plurality of types of filling materials filled in the through holes of the ceramic laminate are (a) a semiconductor ceramic material mainly composed of ZnO, (b) at least one of Sr and Ba, and at least of Mn and Co. A junction-type voltage-dependent resistor according to any one of claims 10 to 11, characterized in that a potential barrier is formed at the junction between the two rare earth oxide materials. .

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