WO2005059928A1

WO2005059928A1 - Semiconductor ceramic electronic component and method for manufacturing same

Info

Publication number: WO2005059928A1
Application number: PCT/JP2004/018941
Authority: WO
Inventors: Kazutaka Nakamura
Original assignee: Murata Manufacturing Co.,Ltd.
Priority date: 2003-12-19
Filing date: 2004-12-17
Publication date: 2005-06-30
Also published as: JPWO2005059928A1; JP4466567B2

Abstract

Disclosed is a simple, small-sized, high-performance semiconductor ceramic electronic component with high reliability and sufficient insulation which can be produced by a laminating process or integral firing process. A semiconductor ceramic electronic component comprises a bonded structure (ceramic element) (24) wherein a semiconductor ceramic body (22) mainly containing ZnO is surface-bonded to a metal oxide body (23) which forms a potential barrier with ZnO, internal electrodes (25a, 25b) which are arranged in such a manner that a current passes through the junction surface of the bonded structure (24), an insulating body (21) containing at least either of an oxide containing Sr and W and an oxide containing Zn and Ti, and external electrodes (26a, 26b) which are so formed on the surface of the insulating body as to be electrically connected to the internal electrodes (25a, 25b).

Description

Specification

Semiconductor ceramic electronic component and method of manufacturing the same

Technical field

The present invention relates to a semiconductor ceramic electronic component and a method of manufacturing the same, and more particularly, to a semiconductor ceramic electronic component manufactured using a laminating method and an integrated firing method, and particularly using a semiconductor ceramic body containing Zn〇 as a main component. The present invention relates to an electronic component and a method for manufacturing the same.

Background art

[0002] In recent years, ceramic electronic components have been required to be miniaturized due to the demand for mounting on a substrate, and chip-type or multilayer ceramic electronic components in which a ceramic layer and an internal electrode layer are laminated are widely used. ing.

Above all, laminated voltage non-linear resistors (hereinafter simply referred to as “non-linear resistors”) have recently been widely used as noise protection elements in the mobile phone and other communication equipment markets. In the field of these communication devices, as a characteristic required for noise protection, a capability to suppress a voltage with a large surge withstand voltage and a low voltage is being demanded. In addition, there is an increasing demand for suppressing current leakage during mounting in order to respond to environmental issues and to reduce power consumption. In addition, as the density of circuits increases, devices with smaller size and higher performance will be required, and with the increase in the number of electronic devices, lower cost components will be required. It has become.

[0003] In such a miniaturized device, it is natural that the distance between external electrodes becomes small, and a current flows on the surface of the device and immediately after soldering, particularly in a varistor which is a semiconductor device. There is a problem related to the insulation of the element surface, which is susceptible to surface reduction due to flux at the time and surface discharge due to surge.

Therefore, a method of covering the surface of the element with glass or a method of insulating the surface of the element by reacting Sb or the like during firing has been proposed.

In the method of covering the element surface with glass while applying force, or the method of insulating the element surface during firing, it is difficult to ensure the uniformity of a surface insulator such as glass, and it is difficult to reduce the size. There is a problem that the more uniform, the lower the uniformity. [0005] Furthermore, since the thickness of the formed insulator is thin, a pinhole is generated immediately and flux or moisture penetrates from the pinhole, causing the element to be corroded or reduced, thereby deteriorating electrical characteristics. There is a problem of causing. On the other hand, if the thickness of the insulator is increased, there is a problem in that the samples are attached (sticking) to each other at the time of firing or at the stage of baking the glass, and the yield is reduced immediately.

[0006] In a method of covering the surface of the element with glass or a method of insulating the surface of the element by reacting Sb or the like during firing, in particular, a non-linear resistor including a ZnO-based semiconductor material is required to reach a grain boundary. There is a problem that the electrical characteristics fluctuate due to the diffusion of the electric current or the like, and particularly immediately affect the breakdown voltage and the limit voltage.

Patent Document 1: JP-A-8-330106

Disclosure of the invention

Problems to be solved by the invention

[0007] The present invention solves the above-mentioned problems, and can be manufactured by using a lamination method and an integral firing method, is simple, has sufficient insulating properties, is small, has high performance, and is reliable. It is an object to provide a semiconductor ceramic electronic component having high performance and a method for manufacturing the same.

Means for solving the problem

[0008] In order to solve the above problems, a semiconductor ceramic electronic component of the present invention (claim 1) includes: a ceramic element using a semiconductor ceramic body; an electrode electrically connected to the ceramic element; A semiconductor ceramic electronic component comprising: an insulator disposed so as to cover at least a portion where the electrode is not formed,

The insulator is characterized in that the insulator contains at least one of an oxide containing Sr and W and an oxide containing Zn and Ti.

[0009] The semiconductor ceramic electronic component of claim 2 is characterized in that the semiconductor ceramic body is a semiconductor ceramic body containing ZnO as a main component.

[0010] The semiconductor ceramic electronic component of claim 3 is

An insulator containing at least one of an oxide containing Sr and W, and an oxide containing Zn and Ti; A semiconductor ceramic body containing ZnO as a main component and a metal oxide compound body that forms a potential barrier with ZnO are arranged inside the insulator,

An internal electrode disposed inside the insulator so that a conductive path passes through a joint surface of the joined body;

And an external electrode disposed on the surface of the insulator and electrically connected to the internal electrode.

[0011] The semiconductor ceramic electronic component of claim 4 is

An insulator containing at least one of an oxide containing Sr and W, and an oxide containing Zn and Ti;

A semiconductor ceramic body disposed inside the insulator, having Zn〇 as a main component and having a resistor property;

An internal electrode disposed inside the insulator so that a conductive path passes through the semiconductor ceramic body;

[0012] The semiconductor ceramic electronic component of claim 5 is

The oxide containing Sr and W is SrWO or a mixed crystal of SrWO and W〇, and the oxide containing Zn and Ti is at least one of ZnTiO and ZnTiO.

It is characterized by.

[0013] Further, in the semiconductor ceramic electronic component of claim 6, when the insulator contains both ZnTiO and ZnTiO, the total content of ZnTiO and ZnTiO is 90 mol% or more; When containing either Zn TiO or ZnTiO, Zn

It is characterized in that the content of either one of TiO and ZnTiO is 90 mol% or more.

[0014] Further, the method for manufacturing a semiconductor ceramic electronic component of the present invention (claim 7)

Inside an insulator containing at least one of an oxide containing Sr and W, and an oxide containing Zn and Ti, a semiconductor ceramic body containing ZnO as a main component, and a potential barrier with ZnO are formed. A bonded body in which the metal oxide compound to be formed is bonded by a surface is provided, and an internal electrode is provided in such a manner that a conductive path passes through the bonded surface of the bonded body; A method for manufacturing a semiconductor ceramic electronic component having a structure in which an external electrode conducting to the internal electrode is provided on a surface of the semiconductor ceramic electronic component,

(a) The ceramic green sheet serving as the insulator, which mainly includes an insulator material containing at least one of oxides containing Sr and W, and oxides containing Zn and Ti, has through holes at predetermined positions. A step of preparing a ceramic green sheet in which is formed and a ceramic green sheet in which a through hole is not formed;

(b) filling a through-hole of the ceramic green sheet having the through-hole formed therein with a semiconductor ceramic paste obtained by converting a semiconductor ceramic powder containing Zn〇 as a main component into a paste;

(c) A metal oxide compound paste in which a metal oxide compound powder mainly composed of a powder of a metal oxide compound forming a potential barrier with Zn〇 is pasted into a through hole of a ceramic green sheet having a through hole formed therein. Filling step;

(d) preparing a ceramic green sheet provided with a conductor pattern for forming an internal electrode;

(e) a ceramic green sheet in which a through hole is filled with a semiconductor ceramic paste, a ceramic green sheet in which a through hole is filled with the metal oxide compound paste, and a ceramic green sheet in which a conductor pattern is provided. Forming a laminate by laminating a ceramic green sheet having holes formed therein;

(f) firing the laminate, inside, a semiconductor ceramic body containing Zn〇 as a main component, and a bonded body in which a metal oxide compound body that forms a potential barrier with ZnO is bonded to the surface, Forming an insulator with internal electrodes arranged in such a manner that the conductive path passes through the joint surface of the body; and

(g) forming an external electrode on the surface of the insulator so as to be electrically connected to the internal electrode.

Further, the method for manufacturing a semiconductor ceramic electronic component of the present invention (claim 8)

Contains at least one of oxides containing Sr and W, and oxides containing Zn and Ti A semiconductor ceramic body having ZnO as a main component and having varistor characteristics is provided inside the insulator, and an internal electrode is provided in such a manner that a conductive path passes through the semiconductor ceramic body; and A method of manufacturing a semiconductor ceramic electronic component having a structure in which an external electrode conducting to the internal electrode is provided on a surface of an insulator,

(b) filling a through-hole of the ceramic green sheet having the through-hole formed therein with a semiconductor ceramic paste obtained by converting a semiconductor ceramic powder having varistor characteristics into a paste;

(c) a step of preparing a ceramic green sheet provided with a conductor pattern for forming an internal electrode;

(d) Laminating and laminating a ceramic green sheet in which a through hole is filled with a semiconductor ceramic paste, a ceramic green sheet in which a conductor pattern is provided, and a ceramic green sheet in which a through hole is formed. Forming a body;

(e) firing the laminate to form an insulator having a semiconductor ceramic body having varistor characteristics and an internal electrode disposed in such a manner that a conductive path passes through the semiconductor ceramic body; Forming,

(f) forming an external electrode on the surface of the insulator so as to conduct with the internal electrode.

[0016] A method for manufacturing a semiconductor ceramic electronic component according to claim 9 is characterized in that:

The oxide containing Sr and W is SrWO, or a mixed crystal of SrW〇 and W〇, and the oxide containing Zn and Ti is at least one of ZnTiO and ZnTi と.

It is characterized by.

[0017] A method for manufacturing a semiconductor ceramic electronic component according to claim 10 is characterized in that:

As the insulator material constituting the ceramic green sheet serving as the insulator, Sr or Using calcined powders obtained by pre-calcining oxides containing W and W, and oxides containing Zn and Ti at 900 ° C to 1100 ° C,

The semiconductor ceramic powder and the metal oxide compound powder constituting the semiconductor ceramic paste and the metal oxide compound paste to be filled in the through holes were preliminarily calcined at 900 ° C to 1100 ° C as the semiconductor ceramic powder and the metal oxide compound powder. Using calcined powder

It is characterized by.

[0018] In the method for manufacturing a semiconductor ceramic electronic component according to claim 11, the insulator is made of ZnTi.

2

If both 〇 and ZnTiO are contained, the total content of Zn TiO and ZnTiO

4 3 2 4 3

When the force is S90mol% or more and contains either ZnTiO or ZnTiO

2 4 3

Requires that the content of either Zn TiO or ZnTiO be 90 mol% or more.

2 4 3

Features.

The invention's effect

[0019] The semiconductor ceramic electronic component of the present invention (claim 1) includes a ceramic element using a semiconductor ceramic body, an electrode that conducts with the ceramic element, and at least one of the ceramic elements formed with an electrode. In a semiconductor ceramic electronic component having an insulator disposed so as to cover a portion thereof, the insulator contains at least one of an oxide containing Sr and W, and an oxide containing Zn and Ti as an insulator. Therefore, it is possible to obtain a semiconductor ceramic electronic component that has reliable surface insulation, has high environmental resistance, and has high resistance to the flux used during soldering.

The insulator containing at least one of oxides containing Sr and W, and oxides containing Zn and Ti used in the semiconductor ceramic electronic component of the present invention (claim 1) is a ZnO-based material, The feature is that the ZnO sintered body does not easily diffuse into each other even when heat or electricity is applied.

That is, the above-mentioned insulator is subjected to current or sintering during sintering or to, for example, a bonded body in which a semiconductor ceramic body containing ZnO as a main component and a metal oxide compound body that forms a potential barrier with ZnO are bonded in a plane. It has good characteristics to prevent mutual diffusion even when voltage is applied. By using such an insulator, highly reliable semiconductor ceramic electronic components (for example, non-linear resistor Etc.) can be obtained.

[0020] Further, by using a semiconductor ceramic body containing ZnO as a main component as the semiconductor ceramic body as in the semiconductor ceramic electronic component of claim 2, it becomes possible to secure required semiconductor characteristics. The invention can be made more effective.

[0021] The semiconductor ceramic electronic component according to claim 3 is a semiconductor ceramic body containing ZnO as a main component in an insulator containing at least one of an oxide containing Sr and W, and an oxide containing Zn and Ti. And a metal oxide compound that forms a potential barrier, and a bonded body (ceramic element) in which the conductive path passes through the bonded surface of the bonded body. In addition, since the external electrodes that conduct to the internal electrodes are arranged on the surface of the insulator, it has reliable surface insulation, and has high environmental resistance and resistance to flux used during soldering. For example, a semiconductor ceramic electronic component such as a non-linear resistor can be obtained.

Further, an insulator containing at least one of an oxide containing Sr and W, and an oxide containing Zn and Ti can form a potential barrier with ZnO, for example, a metal such as Pt, or a general formula: Metal oxide compound represented by MA BO (M is a rare earth element, A is Sr and Ba

13

At least one, B is at least one of Mn and Co, and X is greater than 0 and metal oxide compound such as 0.4 or less). For example, it is possible to obtain a semiconductor ceramic electronic component having a high resistance, such as a nonlinear resistor.

In the case where the insulator reacts with Zn and Ti, the insulator is resistant to acids and alkalis as compared with a semiconductor ceramic containing ZnO as a main component. Electrode plating and electroless plating can be adequately dealt with, which is preferable.

As a metal oxide compound forming a potential barrier with Zn〇, as described above, the general formula: M

1-x

A is represented by A BO, where M is a rare earth element and A is at least 3 of Sr and Ba

On the other hand, it is desirable to use a metal oxide compound in which B is at least one of Mn and Co and is larger than the X force SO and not more than 0.4. In addition, it is possible to obtain a semiconductor ceramic electronic component having desired characteristics. [0024] Examples of the metal oxide compound that is preferably used in the semiconductor ceramic electronic component of the present invention include La Sr MnO. Contains Sr

13

Accordingly, the resistance becomes low, so that the non-linearity in the high current region can be improved.

In addition, the value of X in M ABO reduces the resistance of the metal oxide

Three

From the viewpoint of improving the suppression capability and improving the resistance to transient voltages such as surges, it is desirable that the value be larger than 0 and 0.4 or less. When the value of X exceeds 0.4, it becomes difficult to integrally sinter with Zn 、, and it becomes difficult to obtain sufficient bonding properties between Zn〇 and the metal oxide compound.

[0025] The semiconductor ceramic electronic component according to claim 4 is characterized in that an insulator containing at least one of an oxide containing Sr and W, and an oxide containing Zn and Ti contains ZnO as a main component and a varistor characteristic. And an internal electrode is disposed inside the insulator so that the conductive path passes through the semiconductor ceramic body having varistor characteristics, and the surface of the insulator is electrically connected to the internal electrode. Since external electrodes are provided, they have reliable surface insulation, and have high resistance to environment and flux used during soldering. It becomes possible to obtain parts. In addition, since an insulator containing at least one of an oxide containing Sr and W and an oxide containing Zn and Ti is used as an insulator, a semiconductor having varistor characteristics when sintering a laminated body is used. It is possible to obtain a highly reliable semiconductor ceramic electronic component such as a non-linear resistor, for example, which has good characteristics to prevent mutual diffusion even when a current 'voltage is applied to the ceramic body.

[0026] Further, as in the semiconductor ceramic electronic component of claim 5, as the oxide containing Sr and W constituting the insulator, Zn and Ti are used by using SrWO or a mixed crystal of SrWO and WO.

4 4 3

By using at least one of Zn Ti〇 and ZnTiO as the oxide containing,

2 4 3

It is possible to obtain a highly reliable semiconductor ceramic electronic component having good characteristics in which environmental resistance and resistance to flux used at the time of soldering are large, and to make the present invention more effective. .

In particular, when a mixed crystal containing SrWO and W 用い is used, the presence of SrWO causes the melting of WO.

4 3 4 3 The point drops and becomes the liquid phase. As a result, even if cracks occur in the firing process, Around the characteristic part of the non-linear resistor

Three

As a result, a reliable insulator composition can be formed, and a semiconductor ceramic electronic component having excellent weather resistance can be obtained. In addition, since penetration of plating liquid or the like can be prevented, it is possible to reliably cope with electrolytic plating and electroless plating of the external electrode. Note that w

O has a very high melting point, but the presence of SrWO lowers the liquidus temperature.

3 4

The following effects are obtained. Therefore, SrW〇 containing a small amount of W〇 is insulated

It is suitable as a material of 34 bodies.

In addition, when SrW として is used as the insulator material, the stray capacitance is reduced, and the insulator is induced.

Four

Since the electric conductivity is less than or equal to ₈ measured, it is possible to design a low-voltage, small-capacitance element, and to cope with an increase in the frequency of the circuit.

[0027] Further, as in the semiconductor ceramic electronic component of claim 6, the insulator is made of ZnTiO and ZnTiO.

If both are contained, the total content of ZnTiO and ZnTiO should be 90 mol%

2 4 3

As described above, when one of Zn TinO and ZnTiO is contained, Zn TiO

2 4 3 2

By setting the content of either O or ZnTiO to 90 mol% or more,

4 3

In fact, it is possible to obtain a highly reliable semiconductor ceramic electronic component that has excellent characteristics such as high environmental resistance and resistance to flux used during soldering.

Other substances that can be contained in the insulator include substances that are unlikely to react with semiconductor ceramics containing ZnO as a main component and have a sintering temperature higher than that of semiconductor ceramics containing Zn〇 as a main component. For example, ZrO and Zn TiO are exemplified.

2 2 4

The

If ZnO, TiO, etc. are present in the insulator at a rate exceeding 10 mol%,

2

In other words, when both ZnTiO and ZnTiO are contained, ZnTiO and ZnTiO

2 4 3 2 4 3 The total content is less than 90 mol% and contains either ZnTiO or ZnTiO.

2 4 3

The content of either Zn TiO or ZnTiO is less than 90 mol%

2 4 3

In such a case, the insulation resistance is lowered and corrosion due to the flux at the time of soldering is caused. Also, ZnO and the like may cause defects due to energy generated by current pulses such as ESD, which is not preferable.

Further, the method for manufacturing a semiconductor ceramic electronic component according to the present invention (claim 7) is characterized in that A ceramic green sheet having a through hole at a predetermined position mainly composed of a body material and a ceramic green sheet having no through hole are prepared. A powder of a metal oxide compound which forms an electric potential barrier with Zn〇 is filled in a through hole of a ceramic green sheet in which a semiconductor ceramic paste containing Zn〇 as a main component is filled and another through hole is formed. A ceramic green sheet in which a metal oxide compound paste as a main component is filled and a conductor pattern is provided is prepared.A ceramic green sheet in which a semiconductor ceramic paste is filled in a through hole, and a metal oxide compound in a through hole. A ceramic green sheet filled with paste, a ceramic green sheet provided with a conductor pattern, A ceramic green sheet with no holes formed is laminated and fired, and a semiconductor ceramic body containing ZnO as a main component and a metal oxide compound body that forms a potential barrier with ZnO are bonded inside by surface. An insulator having a body (ceramic element) and internal electrodes arranged in such a manner that a conductive path passes through the joint surface of the joined body is formed, and an outer surface is formed on the surface so as to conduct with the internal electrodes. An electrode is formed. By this manufacturing method, a semiconductor ceramic body containing ZnO as a main component and a potential barrier between ZnO and an oxide containing at least one of an oxide containing Sr and W and an oxide containing Zn and Ti are formed. A bonded body (ceramic element) in which the metal oxide compound to be formed is bonded by a surface is provided, and an internal electrode is provided in such a manner that a conductive path passes through the bonded surface of the bonded body. In addition, it has a structure in which an external electrode that is electrically connected to the internal electrode is disposed on the surface of the insulator, and has high environmental resistance and resistance to flux used for soldering. It becomes possible to obtain semiconductor ceramic electronic components such as bodies. In addition, since an insulator containing at least one of an oxide containing Sr and W, and an oxide containing Zn and Ti is formed as an insulator, the insulator may be used when sintering the laminated body, When current and voltage are applied to a joined body consisting of a semiconductor ceramic body composed mainly of ZnO and a metal oxide compound body that forms a potential barrier with ZnO, mutual diffusion does not occur, resulting in good characteristics and reliability. It is possible to manufacture semiconductor ceramic electronic components with high cost.

Further, in the present invention, a laminated body formed by the laminating method is integrally fired to be formed simultaneously with an internal element and an insulator disposed around the element. Therefore, it is possible to form an insulator that has a sufficient thickness to ensure surface insulation and weather resistance, and that does not have thickness variations as seen when a conventional glass insulating layer is used. Will be possible.

In addition, it is possible to efficiently manufacture semiconductor ceramic electronic components with excellent environmental resistance and flux resistance, and because the laminated body formed by the laminating method is integrally fired, it can be used for miniaturization. As soon as possible, it will be possible to efficiently manufacture small, high-performance and highly reliable semiconductor ceramic electronic components.

Further, by using a material containing at least one of an oxide containing Sr and W and an oxide containing Zn and Ti as a material forming the insulator, a potential barrier is formed with ZnO, for example, Pt Or a metal oxide compound represented by the general formula: MA BO l 3

(M is a rare earth element, A is at least one of Sr and Ba, B is at least one of Mn and Co, and X is greater than 0 and is 0.4 or less) Since it is possible to form an insulator that is not easily cracked immediately after bonding with a material system, a highly reliable semiconductor ceramic electronic component can be obtained.

In the method for manufacturing a semiconductor ceramic electronic component according to the present invention (claim 7), the “ceramic green sheet on which the conductor pattern is provided” means that a through hole is formed at a predetermined position, and the through hole has a semiconductor. The ceramic green sheet may be a ceramic green sheet filled with a ceramic paste or a metal oxide compound paste, or may be a ceramic green sheet having no through holes.

Further, in the method of manufacturing a semiconductor ceramic electronic component according to the present invention (claim 8), a ceramic green sheet having a through hole at a predetermined position mainly composed of the above-described insulator material, and a through hole are formed. No ceramic green sheet was prepared, and the through hole of the ceramic green sheet having the through hole was filled with a semiconductor ceramic paste obtained by pasting a semiconductor ceramic powder having varistor characteristics, and a conductor pattern was provided. A ceramic green sheet is prepared, and a ceramic green sheet in which a through hole is filled with a semiconductor ceramic paste, a ceramic green sheet in which a conductor pattern is provided, and a ceramic green sheet in which a through hole is not formed are laminated and fired. And a semiconductor ceramic body having varistor characteristics inside. , Aspects such as conductive path passes through a semiconductor ceramic body An insulator having the internal electrode provided in the above is formed, and an external electrode is formed on the surface thereof so as to conduct with the internal electrode. As a result, a semiconductor ceramic body having ZnO as a main component and relister characteristics is disposed inside an insulator containing at least one of an oxide containing Sr and W and an oxide containing Zn and Ti. And a structure in which an internal electrode is provided in such a manner that a conductive path passes through the semiconductor ceramic body, and an external electrode which is electrically connected to the internal electrode is provided on the surface of the insulator. For example, it is possible to obtain a semiconductor ceramic electronic component such as a non-linear resistor having high environmental performance and high resistance to a flux used in soldering. In addition, since an insulator containing at least one of an oxide containing Sr and W and an oxide containing Zn and Ti is formed as an insulator, the insulator may be used when sintering a laminated body, Even when a current or voltage is applied to a semiconductor ceramic body having a high reliability, it is possible to efficiently manufacture highly reliable semiconductor ceramic electronic components that have good characteristics to prevent mutual diffusion. Since an insulator containing at least one of oxides containing Sr, W, and oxides containing Zn and Ti is formed, when sintering the laminated body, Zn〇 Even if a current 'voltage is applied to a bonded body in which a metal oxide compound that forms a potential barrier with the semiconductor ceramic body to be formed and ZnO has a surface, mutual diffusion does not occur even when a current is applied, and the characteristics are good and reliable. Semiconductor ceramic electronics It is possible to manufacture the goods. In addition, since the insulator with the elements disposed inside is formed by the laminating method and integrated firing, it has a necessary and sufficient thickness to ensure surface insulation and weather resistance. In addition, it is possible to form an insulator that does not vary in thickness as seen when using a conventional glass insulating layer, and to efficiently produce semiconductor ceramic electronic components with excellent environmental resistance and flux resistance. It can be manufactured.

In the method for manufacturing a semiconductor ceramic electronic component according to the present invention (claim 8), the “ceramic green sheet on which the conductor pattern is provided” means that a through hole is formed at a predetermined position, and the through hole is formed in the through hole. The ceramic green sheet may be a ceramic green sheet filled with a semiconductor ceramic paste obtained by pasting a semiconductor ceramic powder having a lister characteristic, or may be a ceramic green sheet having no through-hole formed therein. Further, as in the method for manufacturing a semiconductor ceramic electronic component according to claim 9, SrWO or a mixed crystal of SrWO and W〇 is used as the oxide containing Sr and W constituting the insulator. , Z

4 4 3

At least one of ZnTiO and ZnTiO may be used as the oxide containing n and Ti.

2 4 3

As a result, it is possible to reliably manufacture a highly reliable non-linear resistor having excellent characteristics such as high environmental resistance and resistance to the flux used in soldering, and the invention of the present application is more effective. It becomes possible to summarize.

When the cracks occur in the firing process by lowering the 4 3 4 3 point and becoming a liquid phase, WO enters the cracks and performs the self-repairing function, so that the cracks around the characteristic portion of the nonlinear resistor

Three

A reliable insulator composition can be formed, and a semiconductor ceramic electronic component having excellent weather resistance can be obtained. In addition, since penetration of plating liquid and the like can be prevented, it is possible to efficiently manufacture semiconductor ceramic electronic components that can reliably cope with electrolytic plating and electroless plating of external electrodes. .

[0031] Further, as in the method for manufacturing a semiconductor ceramic electronic component according to claim 10, as an insulator material constituting a ceramic green sheet to be an insulator, an oxide containing Sr and W, an oxide containing Zn and Ti, Using a calcined powder preliminarily calcined at 900 ° C to 1100 ° C, the semiconductor ceramic paste and the metal oxide compound powder constituting the semiconductor ceramic paste and metal oxide compound paste filled in the through-holes are used as semiconductor powder. By using a calcined powder obtained by calcining ceramic powder and metal oxide compound powder in advance at 900 ° C to 1100 ° C, it is possible to mix between different materials (insulator material and semiconductor ceramic or metal oxide compound) during sintering. Between them) can be prevented from occurring. At the same time, it is possible to suppress shrinkage during sintering and prevent the occurrence of structural defects such as cracks. Furthermore, it is possible to manufacture a highly reliable semiconductor ceramic electronic component having good characteristics such as high environmental resistance and high resistance to flux used in soldering.

[0032] Further, as in the method for manufacturing a semiconductor ceramic electronic component according to claim 11, the insulator is made of ZnT.

2 When both i〇 and ZnTiO are contained, the total content of Zn TiO and ZnTiO

When the 4 3 2 4 3 ratio is 90 mol% or more and either Zn TiO or ZnTiO is contained

2 4 3

The content of either ZnTiO or ZnTiO should be 90 mol% or more. In this case, it is possible to more reliably obtain a highly reliable semiconductor ceramic electronic component having good characteristics in which the environment resistance and the resistance to the flux used in soldering are large.

Brief Description of Drawings

[FIG. 1] (a)-(g) are diagrams for explaining a method of manufacturing a semiconductor ceramic electronic component (non-linear resistor) according to an embodiment of the present invention.

FIG. 2 (a) is a diagram for explaining a method of forming a crimp block (mother-laminate) by a lamination method in a method of manufacturing a semiconductor ceramic electronic component (non-linear resistor) which is useful in an embodiment of the present invention. And (b) is a cross-sectional view showing the internal structure of the formed crimp block (mother laminate).

FIG. 3 is a cross-sectional view showing a structure of an element obtained by cutting a crimp block and dividing the crimp block.

FIG. 4 is a cross-sectional view showing a structure of a semiconductor ceramic electronic component (non-linear resistor) manufactured by a method for manufacturing a semiconductor ceramic electronic component (non-linear resistor) according to an embodiment of the present invention.

FIG. 5 (a) is a diagram for explaining a method of forming a crimp block (mother-laminate) by a laminating method in a method of manufacturing a semiconductor ceramic electronic component (non-linear resistor) which is useful in an embodiment of the present invention. (B) is a cross-sectional view showing the internal structure of the formed crimp block (mother laminate).

FIG. 6 is a cross-sectional view showing a structure of an element obtained by cutting a crimp block and dividing the crimp block.

FIG. 7 is a cross-sectional view showing a structure of a semiconductor ceramic electronic component (non-linear resistor) manufactured by a method of manufacturing a semiconductor ceramic electronic component (non-linear resistor) according to an embodiment of the present invention.

FIG. 8 is a cross-sectional view showing a configuration of a semiconductor ceramic electronic component (non-linear resistor) (Comparative Sample X) manufactured for comparison.

FIG. 9 is a cross-sectional view showing a configuration of a semiconductor ceramic electronic component (non-linear resistor) (comparative sample Y) manufactured for comparison.

Explanation of symbols

[0034] 1 Ceramic green sheet (insulating sheet) la Zn〇 paste filling sheet

lb LSMO paste filling sheet

LC ZnO varistor material paste filling sheet

2 Through hole

3 Zn〇 paste

4 Metal oxide compound paste (LSMO paste)

5 Pt paste (conductor pattern for internal electrode formation)

6, 16 Crimping block (one mother laminate)

7, 17 elements (fired precursor)

7a, 17a Fired element (sintered body)

13 ZnO varistor material paste

21 Insulator

22 Semiconductor ceramic body

23 Metal oxide compound forming a potential barrier with ZnO

24 Joint (Ceramic element)

25a, 25b Internal electrode

26a, 26b External electrode

27 Semiconductor ceramic body with varistor characteristics

BEST MODE FOR CARRYING OUT THE INVENTION

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

Example

[0036] In this example, as shown below, a mother laminate having a plurality of internal elements is formed, and this is cut and divided into individual elements. A semiconductor ceramic electronic component (non-linear resistor in this example) having a length of 1. Omm, a width of 0.5 mm and a thickness of 0.5 mm was manufactured.

(1) Preparation of Ceramic Green Sheet for Forming Insulator

The ceramic green sheet mainly composed of an insulator material for forming the insulator is shown below. It was produced by the method described above.

About 1 / im diameter of SrCO powder and about 2 μm diameter of WO powder were added to each element ratio of Sr and W.

3 3

1 · 0: 1.0, 1 · 0: 1.1, 1 · 0: 1 · 2 at the ratio of each. Then, pure water was added to the prepared powder at a ratio of 1 to 1 of the total weight of the powder, PSZ beads having a diameter of 2 mm were further added, and the mixture was pulverized and mixed with a ball mill for 50 hours to prepare a ceramic slurry. did.

[0038] Then, the water in the ceramic slurry was evaporated at 150 ° C to obtain SrWO powder and SrWO powder.

Four

A mixed crystal powder of wo and wo (raw material powder) was obtained.

4 3

Also, ZnO powder with a diameter of about 0.5 μm and TiO (rutile) powder with a diameter of about 0.4 μm

2

Compounds were prepared at an elemental ratio of 1.0: 1.0, 1.5: 1.0, 2.0: 1.0, 2.5: 1.0, respectively. Then, pure water is added to the prepared powder at a ratio of 1 to 1 of the total weight of the powder, PSZ beads having a diameter of 2 mm are further added, and the mixture is pulverized and mixed with a ball mill for 50 hours. Was prepared. Then, the water in the ceramic slurry was evaporated at 150 ° C. and dried to obtain an oxide powder (raw material powder) containing Zn and Ti.

Next, the raw material powder obtained as described above (powder of SrWO crystal, a mixture of SrWO and WO)

443 crystal powder and oxide powder containing Zn and Ti) were calcined at 900-1100 ° C for 2 hours, and the calcined powder obtained was coarsely ground with a pulverizer and then calcined. Pure water was added at a 1: 1 ratio to the powder. After that, powder of SrWO crystal, powder of mixed crystal of SrWO and WO

4 4 3

Then, it was pulverized again with PSZ beads having a diameter of 2 mm until the average particle diameter became 0.7 / im. Similarly, an oxide powder containing Zn and Ti was pulverized until the average particle size became 0.5 μπι. Then, the obtained slurry was dehydrated and dried, and ethanol, toluene, and a dispersing agent were added to disperse the slurry.

[0040] Then, after the obtained slurry is dehydrated and dried, ethanol, toluene, and a dispersing agent are added to and dispersed in the raw material, and a binder and a plasticizer are added to form a slurry. A 50-zm-thick ceramic green sheet (hereinafter also referred to as “insulating sheet”) was produced. Then, as shown in FIG. 1 (a), a through hole 2 having a diameter of 200 μm was formed in a predetermined ceramic green sheet (insulating sheet) 1 by a laser.

[0041] The above-mentioned SrWO powder and the mixed crystal powder of SrWO and W〇 were used for the insulator. When used, it is a substance that does not easily react with the semiconductor ceramic containing ZnO as a main component and has a sintering temperature higher than that of the semiconductor ceramic containing ZnO as a main component, such as ZnTi〇.

It is possible to include 24 powder.

When an oxide powder containing Zn and Ti is used for the insulator, ZrO or the like is used.

2 It is also possible to include a powder.

(2) Preparation of Semiconductor Ceramic Paste Containing ZnO as Main Component

0.005 mol of Al O in Zn〇. After adding / _o and pure water, PSZ beads with a diameter of 2mm

twenty three

Was ground and mixed by a ball mill for 50 hours. After the water in the slurry was evaporated and dried, it was calcined at 900-1000 ° C for 2 hours. Pure water was added to the calcined material at a ratio of 1: 1 and pulverized using PSZ beads having a diameter of 2 mm until the average particle size became about 0.5 μm. Then, the slurry thus obtained is dehydrated and dried, and then a solvent, a varnish, and the like are added to the obtained powder (semiconductor ceramic powder containing ZnO as a main component), followed by paste rubbing. Thus, a semiconductor ceramic paste containing Zn〇 as a main component (hereinafter, also simply referred to as “Zn〇 paste”) was obtained.

(3) Preparation of Metal Oxide Compound Paste Forming Potential Barrier with ZnO

La O, SrCO, and Mn O are each monoliths]; so that they become 0.35, 0.3, 1.0

2 3 3 3 4

After weighing in an appropriate ratio and wet-mixing with a ball mill, the mixture was evaporated to dryness, heat-treated at 1000 ° C., and temporarily reacted.

The reaction product thus obtained is once ground in a ball mill until the average particle size becomes 1 μm or less, and a solvent and a varnish are added and paste-ridden to form a metal oxide compound that forms a potential barrier with ZnO. A paste was obtained.

In the following, La, Sr, and Mn reaction oxides are abbreviated as “LSMO”.

(4) Preparation of ZnO Varistor Material Paste

0.005 mol% of Al O in Zn〇, 1 mol% of PrO, 0.1 mol% of CaCO, 0.1 Olmol of K (OH)

2 3 6 11 3

%, Pure water was added, and the mixture was pulverized and mixed in a ball mill using PSZ beads having a diameter of 2 mm for 50 hours.

After the water content of the slurry was evaporated and dried, the slurry was calcined at 900 to 1000 ° C. for 2 hours. Pure water is added to this calcined material at a ratio of 1: 1 and the average particle size is reduced using PSZ beads with a diameter of 2 mm. Crushed to about 0.5 / m. Then, the slurry obtained in this manner is dewatered and dried, and then a solvent, a varnish, etc. are added to the obtained powder, and the paste is pasteurized to obtain a semiconductor ceramic paste having Zn〇 as a main component and having varistor characteristics. (Hereinafter simply referred to as “Zn〇 varistor material paste”).

[0045] (5) Filling of paste into through-holes of ceramic green sheet

As shown in FIG. 1 (b), the through hole 2 of the ceramic green sheet (insulating sheet) 1 for forming an insulator prepared in (1) above is filled with the Zn〇 paste 3 prepared in (2) above. At the same time, as shown in Fig. 1 (c), the metal oxide compound paste prepared in (3) above is inserted into the through holes 2 of the ceramic green sheet (insulated sheet) 1 for insulator formation prepared in (1) above. (LSMO paste) 4 was filled by a screen printing method, and dried to prepare a Zn〇 paste-filled sheet 1 (la) and an LSMO paste-filled sheet 1 (lb).

Further, as shown in FIG. 1 (d), the through-hole 2 of the ceramic green sheet (insulating sheet) 1 for forming an insulator prepared in (1) above was formed in the above-described (4). A Zn〇 varistor material paste-filled sheet 1 (lc) was prepared by filling the ZnO paste material paste 13.

(6) Internal electrode printing on ceramic green sheet

As shown in Figs. 1 (e) and (f), of the ZnO paste-filled sheet 1 (la) and LSMO paste-filled sheet l (lb) prepared in (5) above, A Pt paste (conductor pattern for forming internal electrodes) 5 was printed by a screen printing method so as to be electrically connected to the ZnO paste 3 and the LSMO paste 4 filled in 2, and dried.

Further, as shown in FIG. 1 (g), of the Zn スタ varistor material paste-filled sheet 1 (lc) prepared in (5) above, the Zn〇 varistor filled in the through hole 2 was provided on the surface of a predetermined sheet. A Pt paste (conductor pattern for forming internal electrodes) 5 was printed by a screen printing method so as to be electrically connected to the material paste 13 and dried.

[0048] (7) Lamination

Then, as shown in Fig. 2 (a), from the bottom to the top, an insulating sheet 1 with no through holes, an LSMO paste-filled sheet 1 (lb) with a conductive pattern, and a Zn〇ぺ1.96 x 10 ^{6 is} filled and stacked in the following order: Filling sheet 1 (la), LSMO paste filling sheet 1 (1 b) with conductor pattern, and insulating sheet 1 without through holes A crimping block (mother laminated body) 6 as shown in FIG. 2 (b) was prepared by crimping at a pressure of Pa. Also, as shown in FIG. Insulation sheet 1 with no holes, Zn 貫通 varistor material paste filling sheet 1 with through holes 2 filled with Zn〇 varistor material paste 1 (lc), and insulation sheet 1 without through holes 1 Then, pressure bonding was performed at a pressure of 1.96 × 10 ⁶ Pa to produce a pressure-bonded block (mother-laminate) 16 as shown in FIG. 5 (b).

[0049] (8) Cut

As shown in FIGS. 2 (b) and 5 (b), the crimping blocks 6 and 16 prepared in (7) are cut perpendicularly to the lamination surface by a dicer, and the individual elements (fired) are cut. (Precursor) 7 (Fig. 3) and 17 (Fig. 6).

The element 7 shown in FIG. 3 is a bonded body (a ceramic element) in which a semiconductor ceramic body 22 containing ZnO as a main component and a metal oxide compound body 23 forming a potential barrier with ZnO are bonded inside a insulator 21. ) And internal electrodes 25a and 25b arranged in such a manner that the conductive path passes through the joint surface of the joined body 24.

The element 17 shown in FIG. 6 is disposed inside an insulator 21 in such a manner that a semiconductor ceramic body 27 mainly composed of ZnO and having varistor characteristics and a conductive path passes through the semiconductor ceramic body 27. It has a structure having internal electrodes 25a and 25b.

[0050] (9) Firing

The element (firing precursor) 7 in FIG. 3 and the element (firing precursor) 17 in FIG. 6 cut and divided in (8) above were degreased at 600 ° C., and then the element (firing precursor) 7 in FIG. Was fired at 1300 ° C, and the device (firing precursor) 17 in FIG. 6 was fired at 1200 ° C for 3 hours.

(10) Formation of external electrode

Ag—Pd (Ag / Pd weight ratio: 9) was added to both ends of the element (sintered body) fired in (9) above (7a) including the end faces facing each other from which the internal electrodes 25a and 25b were drawn out. / 1) The paste was applied and baked at 900 ° C for 10 minutes to form external electrodes 26a and 26b that are electrically connected to the internal electrodes 25a and 25b, as shown in FIG.

The internal electrodes 25a and 25b of the element (sintered body) 17 (17a) fired in the above (9) are drawn out. Ag-Pd (Ag / Pd weight ratio 9/1) base is applied to both ends including the opposing end surfaces, and baked at 900 ° C for 10 minutes, as shown in Fig. 7. External electrodes 26a and 26b, which are electrically connected to 25a and 25b, were formed.

(11) Preparation of Comparative Sample X

Ethanol, toluene, and a dispersing agent are added to the Zn-based semiconductor ceramic powder prepared in (2) above to form a slurry, and a binder and a plasticizer are formed into a slurry. A 50 μπι thick sheet (ZnO sheet) is prepared by the method, and ethanol, toluene and a dispersing agent are added to the powder of the metal oxide compound prepared in the above (3), and the mixture is dispersed.とした After the slurry, a 50-zm-thick sheet (LSMO sheet) was prepared by the doctor blade method.

[0053] Then, from the bottom to the top, LSMO sheet (10 sheets) _Zn （sheet (10 sheets)-LSMO sheet (10 sheets) are laminated and crimped in this order, and a block having a thickness of 1.18 mm is formed. The shape was cut to a size of 0.58mm X 0.58mm. That power, 600. C to escape from the moon, 1250. 3B temple with C Γ After firing, apply external electrode paste consisting of Ag / Pd (9/1) to the exposed LSMO material (upper and lower ends) on both upper and lower surfaces after sintering, 900 ° C After forming the external electrodes by baking for 10 minutes, apply a glass paste containing bismuth borosilicate as a main component to the area where the external electrodes are not formed, and bake at 700 ° C for 10 minutes. As shown in FIG. 8, on both sides of a ZnO semiconductor ceramic 31, a metal oxide compound (LSMO) 32 that forms a potential barrier with Zn〇 has a structure in which the metal oxide compound (LSMO) 32 is bonded and disposed. A sample X for comparison was prepared in which the external electrodes 33a and 33b were formed on the exposed surface of the (LSMO) 32, and the portion where the external electrodes 33a and 33b had no force S was covered with the glass layer.

(12) Preparation of Comparative Sample Y

2 3 6 11 3

%, Pure water was added, and the mixture was pulverized and mixed in a ball mill using PSZ beads having a diameter of 2 mm for 50 hours. After the water in the slurry was evaporated and dried, it was calcined at 1000 ° C for 2 hours. Pure water was added to the calcined material at a ratio of 1: 1 and pulverized using PSZ beads having a diameter of 2 mm until the average particle diameter became about 0.5 xm.The obtained slurry was dewatered and dried. . Ethanol, toluene and a dispersant are added to the raw material powder to disperse, and a binder and a plasticizer are added. Then, a sheet having a thickness of 50 / im was produced by a doctor blade method. After printing Pt paste in a predetermined pattern on this sheet, laminating and pressing, cutting to a predetermined size, degreased at 600 ° C, and baked at 1200 ° C for 3 hours, As shown in FIG. 9, an element (sintered body) in which a Pt internal electrode 42 is disposed in a semiconductor ceramic body 41 having Zn〇 as a main component and having varistor characteristics so as to face each other via a semiconductor ceramic layer 43. ) 44 was obtained. Then, an Ag_Pd paste (Ag / Pd (weight ratio) = 9Zl) is applied to both ends of the element (sintered body) 44, including the end faces facing each other from which the Pt internal electrodes 42 are drawn out, and heated at 900 ° C. By baking for 10 minutes, external electrodes 45a and 45b electrically connected to the internal electrode 42 were formed as shown in FIG. Then, a glass paste containing bismuth phosphate as a main component is applied to a region where the external electrodes 45a and 45b are not formed, and baked at 700 ° C. for 10 minutes to form a glass layer 46 for comparison. A sample Y was obtained.

The size of the sample of the present invention was 0.6 × 0.3 × 0.3 mm.

The size of each of the samples of Comparative Example X and Comparative Example Y was 1.0 X 0.5 X 0.5 mm.

[Evaluation of Characteristics]

The following characteristics were examined for the samples of Examples and Comparative Examples manufactured as described above.

(1) Breakdown voltage: V

1mA

(2) Voltage nonlinear coefficient: _α

(3) The ratio of the voltage across the sample when a 1 μΑ DC current is applied to the breakdown voltage V

1mA

: V / V

1 μA 1mA

(4) Capacitance (1 MHz)

(5) Flux resistance

(6) Limit voltage ratio: V / V

1A 1mA

(7) ESD resistance

(8) Life change

Tables 1 and 2 show the measurement results for each characteristic. The data of Comparative Samples X and Y in Table 1 and the data of Comparative Samples X and Y in Table 2 are the same data.

[Table 1] i0057 High resistance Flux resistant voltage Lifetime Characteristic element VlmA Capacitance

No. Material Structure a Property ratio change Material (V)

Sr / W ratio / VlraA (F)

(¾) lA lmA (¾)

1 1.0 / 1.0 LSMO / ZnO A 4.22 35.9 0.83 10.2 +0.3 1.83 -2.5 -0.9

2 1.0 / 1.1 LSMO / ZnO A 4.25 34.7 0.85 10.1 -0.5 1.78 -2.9 +0.2

3 1.0 / 1.2 LSMO / ZnO A 4.24 34.1 0.85 10.2 + 1.0 1.82-2.1-0.6

4 1.0 / 1.0 ZnOA "Lister B 25.6 28.2 0.76 3.7 +1.6 1.75 -6.8 -3.5

5 1.0 / 1.1 ΖηθΛ 'Lister B 25.8 31.6 0.78 3.6 +1.5 1.71 -6.5 -3.2

6 1.0 / 1.2 ΖηΟΛ 'Lister B 24.9 30.8 0.77 3.7 +1.8 1.73 -5.3 -3.2 Comparative sample

7 LSMO / ZnO C 4.02 34.5 0.35 40.5 -45.7 1.68 -65.4 -6.8 X

Comparative sample

8 ZnOA 'Lister D 7.66 19.8 0.32 109.8 -23.6 1.68 -25.9 -8.9

Y

oo σ¾

[0058] In Tables 1 and 2, "structure" means A for the non-linear resistor having the structure shown in FIG. 4, B for the structure shown in FIG. 7, C for the structure shown in FIG. The structure shown in FIG.

[0059] Breakdown voltage: V measures the voltage across the sample when a DC current of 1 mA flows

1mA

Value. [0060] Voltage nonlinear coefficient: α is a value obtained by the following equation from the voltage across the sample and the breakdown voltage when a DC current of 0.1 mA flows.

[0061] V / V measures the voltage across the sample when a DC current of 1 μA flows,

1 a A 1mA

The ratio (V / V) to the down voltage V is obtained.

1mA 1 μA 1mA

Capacitance is the value measured at 1 MHz using an LCR meter.

[0062] The flux resistance was measured using a flux containing PbZSn solder and Br2% in order to check for deterioration during soldering. The change in V before and after immersion was examined.The rate of change (V before immersion / V -1 after immersion) x 100 (%) is shown in Tables 1 and 2 as flux resistance. I have.

Ι β Α

[0063] The limiting voltage ratio: V / V has a triangular waveform of 8 X 20 µs and a current peak of 1 mm.

1A 1mA

Peak voltage when applying a current surge to the sample and measuring the voltage across the sample

1A and breakdown voltage: V ratio: V / V.

1mA 1A 1mA

[0064] The ESD resistance was measured by applying a contact discharge type ESD generator, applying a static electricity of 30kV to both ends of the sample 100 times each, and examining the change in V before and after the application. This rate of change (

Ι μ Α

Tables 1 and 2 show the value of V before application / V -1 after application) Χ 100 (%) as ESD resistance.

1 A 1 A

ing.

[0065] The change in life is as follows: DC voltage 80% of V

1mA

A life test was performed by applying a voltage, and the change in V before and after 1000 hours of application was examined.

Ι μ Α

Change rate (V before application / V -1 after application) として ιοο (%) as life change (%)

Ι μ Α Ι μ Α

And shown in 2.

[0066] The ratios of the Zn and Ti oxide compounds were obtained by using X-ray diffraction after firing. In Table 2, the ratio of Zn TiO / ZnTiO /

2 4 3

The substances that correspond to "others" are mainly Zn〇 and TiO.

2

The proportion of these substances varies depending on the composition ratio at the time of preparation and the calcining temperature (adjusted in the range of 900 to 1100 ° C). However, ZrO can be included as another substance

2

It is.

[0067] Tables 1 and 2 show that samples No. 16 (Table 1) and No. 9 which are samples that are useful for the examples of the present invention. For 18 samples (Table 2), breakdown voltage: V voltage nonlinear coefficient: a,

1mA,

Ratio to breakdown voltage V: V / V, capacitance (1MHz), flux resistance, limit

1mA 1 μA 1mA

Voltage ratio: V / V ESD immunity, lifetime change characteristics, no practical problem

1A 1mA,

It can be seen that is obtained. However, for the comparative samples X and Y, it was found that only unfavorable characteristics could be obtained depending on the measurement items.

No. 16 and No. 17 samples with a total content of Zn TiO and ZnTiO of less than 90 mol%

2 4 3

However, the flux resistance, ESD resistance, life change rate, and the like are slightly unfavorable, and it is desirable that the total content of ZnTiO and ZnTiO should be 90 mol% or more.

2 4 3

Call

As described above, according to the present invention, a non-linear resistor (semiconductor) having a high environmental resistance and a high resistance to a flux used in soldering is obtained by integrally firing the laminate formed by the lamination method. Ceramic electronic components) can be manufactured efficiently.

[0069] Further, since an insulator containing at least one of an oxide containing Sr and W and an oxide containing Zn and Ti is formed as an insulator, the sintering of the laminate is performed. At this time, even when current and voltage are applied to the internal elements, no mutual diffusion occurs, and it is understood that a highly reliable nonlinear resistor having good characteristics and high reliability can be manufactured. In the samples of Nos. 1-6 (Table 1) and Nos. 9-18 (Table 2), which are examples of the present invention, the ESD resistance is good. It is considered that the above-mentioned mutual diffusion was suppressed and prevented.

Further, when a material containing at least one of an oxide containing Sr and W and an oxide containing Zn and Ti is used as a material forming the insulator, a potential barrier is formed with ZnO, for example, Metals such as Pt and metal oxide compounds represented by the general formula: MA BO (

l 3

M is a rare earth element, A is at least one of Sr and Ba, B is at least one of Mn and Co, and X is a metal oxide compound that is larger than 0 and 0.4 or less. Since it is possible to form an insulator which is not easily cracked immediately after bonding with the material system, a highly reliable non-linear resistor can be obtained.

[0070] Further, since the element is surely covered with an insulating layer (insulator), reduction by flux at the time of soldering such as reflow and reduction of electrical characteristics due to residual or permeated flux. It is possible to prevent a decrease and the like, and it is possible to improve environmental resistance such as weather resistance.

In addition, since the element is covered with an insulating layer that is integrally sintered, surface current can be suppressed, leakage current can be reduced, and weather resistance can be improved.

[0071] Furthermore, in the case of coating with a material having a lot of defects such as a glass layer as in the related art, a semiconductor which is partially deposited on the surface easily causes a surface discharge or is easily deteriorated by static electricity. As in the present invention, a mixed crystal containing SrWO and WO is referred to as an insulator material.

4 3

When used in combination, it has good adhesion to metal oxides such as semiconductor ceramics and LSMO containing Zn〇 as the main component, varistor material, etc., and the pores at the interface are filled with the liquid phase of WO.

Three

Therefore, it is possible to reliably suppress surface discharge and suppress deterioration due to static electricity. In particular, the effect is great in the case of a device in which characteristics are obtained at the interface between a ZnO-based semiconductor ceramic and a metal oxide compound such as LSMO.

[0072] When SrWO is used as the insulator material, the stray capacitance is reduced, and the insulator material is used.

Four

Since the dielectric constant is less than or equal to ₈ measured, it is possible to design a low-voltage and small-capacitance element, and it is possible to cope with a high-frequency circuit in a circuit.

In addition, when such a material configuration having a small floating capacitance is used, it is possible to form a multiple element having no (low) crosstalk (for example, an element having a configuration as shown in FIG. 2B). is there.

Industrial applicability

The invention of the present application is directed to a ceramic element using a semiconductor ceramic body, an electrode electrically connected to the ceramic element, and an insulator provided so as to cover at least a portion of the ceramic element where no electrode is formed. In the semiconductor ceramic electronic component having the above, a material containing at least one of an oxide containing Sr and W and an oxide containing Zn and Ti is used as an insulator. It is possible to obtain a semiconductor ceramic electronic component having a surface insulating property and having high environmental resistance and high resistance to flux used during soldering.

Further, according to the method for manufacturing a semiconductor ceramic electronic component of the present invention, a half of A ceramic element using a conductive ceramic body is provided, and for example, a semiconductor ceramic electronic component such as a non-linear resistor can be manufactured using a laminating method and an integrated firing method. Semiconductor ceramic electronic components such as nonlinear resistors with high performance and high reliability can be manufactured efficiently.

Therefore, the semiconductor ceramic electronic component obtained by the present invention, for example, a linearly-coupled antibody, can be widely applied to various uses such as the field of mobile phones and other communication technologies, and the field of electronic devices used for such purposes. It is possible.

Claims

The scope of the claims

[1] A ceramic element using a semiconductor ceramic body, an electrode electrically connected to the ceramic element, and an insulator disposed so as to cover at least a portion of the ceramic element where the electrode is not formed. A semiconductor ceramic electronic component comprising:

A semiconductor ceramic electronic component, wherein the insulator contains at least one of an oxide containing Sr and W and an oxide containing Zn and Ti.

2. The semiconductor ceramic electronic component according to claim 1, wherein the semiconductor ceramic body is a semiconductor ceramic body containing Zn セラミック as a main component.

[3] an insulator containing at least one of an oxide containing Sr and W, and an oxide containing Zn and Ti;

A semiconductor body comprising Zn〇 as a main component and a metal oxide compound body forming a potential barrier with ZnO, which are disposed inside the insulator,

3. The semiconductor ceramic electronic component according to claim 1, further comprising: an external electrode provided on a surface of the insulator, the external electrode being electrically connected to the internal electrode.

[4] an insulator containing at least one of an oxide containing Sr and W, and an oxide containing Zn and Ti;

[5] The oxide containing Sr and W is SrWO or a mixed crystal of SrWO and WO, and the oxide containing Zn and Ti is at least one of ZnTiO and ZnTiO.

The semiconductor ceramic electronic component according to any one of claims 14 to 15, wherein:

[6] When the insulator contains both ZnTiO and ZnTiO, ZnTiO

The total content of 2 4 3 2 4 and ZnTiO is 90 mol% or more, and either ZnTiO or ZnTiO

3 2 4 3 When one of them is contained, the content of either Zn TiO or ZnTiO

2 4 3

16. The semiconductor ceramic electronic component according to claim 15, wherein the content is 90 mol% or more.

[7] Inside an insulator containing at least one of an oxide containing Sr and W and an oxide containing Zn and Ti, a semiconductor ceramic body containing ZnO as a main component and a metal forming a potential barrier with ZnO A joined body in which the oxidized compound body is joined by a surface is provided, and an internal electrode is arranged in such a manner that a conductive path passes through the joining surface of the joined body, and on the surface of the insulator. A method for manufacturing a semiconductor ceramic electronic component having a structure in which an external electrode that is electrically connected to the internal electrode is provided,

(e) a ceramic green sheet having a through hole filled with a semiconductor ceramic paste, a ceramic green sheet having a through hole filled with the metal oxide compound paste, and a ceramic green sheet having a conductor pattern disposed therein. Forming a laminate by laminating a ceramic green sheet having holes formed therein;

(f) firing the laminated body, inside, a semiconductor ceramic body containing Zn〇 as a main component, Zn o and a metal oxide compound that forms a potential barrier are bonded together by a surface, and an insulator including an internal electrode arranged in such a manner that a conductive path passes through the bonding surface of the bonded body. Forming,

(g) forming an external electrode on the surface of the insulator so as to conduct with the internal electrode.

[8] Inside an insulator containing at least one of an oxide containing Sr and W, and an oxide containing Zn and Ti, a semiconductor ceramic body having ZnO as a main component and having a relister characteristic is disposed. In addition, a semiconductor ceramic electronic device having a structure in which an internal electrode is disposed in such a manner that a conductive path passes through the semiconductor ceramic body, and an external electrode that is electrically connected to the internal electrode is disposed on a surface of an insulator. A method of manufacturing a part,

(f) forming an external electrode on the surface of the insulator so as to be electrically connected to the internal electrode.

[9] The oxide containing Sr and W is SrWO or a mixed crystal of SrW〇 and W〇, The oxide containing Zn and Ti is at least one of ZnTiO and ZnTiO.

9. The method for producing a semiconductor ceramic electronic component according to claim 7, wherein:

[10] An oxide containing Sr and W and an oxide containing Zn and Ti were calcined in advance at 900 ° C. and 1100 ° C. as the insulator material constituting the ceramic green sheet serving as the insulator. Using roasted powder,

A method for producing a semiconductor ceramic electronic component according to any one of claims 79, characterized by the following:

[11] When the insulator contains both ZnTiO and ZnTiO, the total content of ZnTiO and ZnTiO is 90 mol% or more, and the insulator contains one of ZnTiO and ZnTiO. The content of either Zn TiO or ZnTiO

11. The method for producing a semiconductor ceramic electronic component according to claim 7, wherein the content is 90 mol% or more.