KR100866478B1 - Electrode paste, ceramic electronic component and method for producing same - Google Patents

Abstract

The present invention provides an electrode paste, a ceramic electronic component, and a method of manufacturing the same, which can suppress the occurrence of bursting.

The manufacturing method of the ceramic capacitor 10 which concerns on this invention exposes the capacitor body 16 by which the dielectric layer 12 and the internal electrode layer 14 were alternately laminated | stacked, and the internal electrode layer 12 of the capacitor body 16 is exposed. Applied to the manufacture of the ceramic capacitor 10 having the external electrode 18 formed on the end face 16a, the end face 16a of the capacitor body 16 is made of Cu powder and Ni having a higher ionization tendency than NiCu. Applying an external electrode paste containing Ni powder, and firing the capacitor body 16 to which the external electrode paste is applied, wherein the weight ratio of Ni powder to Cu powder is 0.5 to 10% by weight, and Since the average particle diameter of Ni powder is 0.2-10 micrometers, generation | occurrence | production of a burst can be suppressed.

Ceramic Capacitor, External Electrode Paste, Fires

Description

Ceramic electronic component and method for manufacturing same {Electrode paste, ceramic electronic component and method for producing same}

The present invention relates to an electrode paste, a ceramic electronic component and a method of manufacturing the same.

Conventionally, in the manufacture of ceramic electronic components such as multilayer ceramic capacitors, a laminate in which a plurality of layers of a layer made of powder of a ceramic dielectric constituting a dielectric layer and a layer made of internal electrode paste constituting an internal electrode layer are alternately formed is provided. After baking a laminated body, the method of providing an external electrode was employ | adopted.

Here, in forming the dielectric layer, a ceramic molded body produced by appropriately drying a dielectric paste obtained by mixing a ceramic dielectric powder, an organic binder, an organic solvent, and the like into a sheet into a sheet form by a doctor blade method or the like is used. In addition, the internal electrode paste used for formation of an internal electrode layer is made into paste form by disperse | distributing metal powders, such as nickel, to an organic binder, an organic solvent, etc. And the above-mentioned laminated body is normally produced by screen-printing the internal electrode paste on the surface of a sheet-shaped ceramic molded object, drying the organic solvent contained in an internal electrode paste, and pressing-molding multiple sheets of this molded object.

The ceramic element is formed by chipping and stacking the laminate. In addition, an external electrode is provided on an end surface of the ceramic element in which the internal electrode layer is exposed. In forming the external electrode, an external electrode paste in which a metal powder such as copper is dispersed in a binder, a solvent, or the like to form a paste is used. That is, after apply | coating this external electrode paste to the end surface of a ceramic element, the ceramic element to which the external electrode paste was apply | coated is baked, and the metal powder in an external electrode paste is sintered, and an external electrode which is a porous sintered compact is formed. Moreover, such an external electrode is disclosed by following patent document 1-patent document 5, etc., for example.

Generally, before soldering a ceramic electronic component to a board | substrate etc., plating process of copper, nickel, tin, etc. is performed on the surface of an external electrode in order to improve connection reliability and wettability.

Patent Document 1: Japanese Patent Application Laid-Open No. 5-275272

Patent Document 2: Japanese Patent Application Laid-Open No. 8-306580

Patent Document 3: Japanese Unexamined Patent Publication No. 2002-198253

Patent Document 4: Japanese Patent Application Laid-Open No. 7-335477

Patent Document 5: Japanese Patent Application Laid-Open No. 10-144559

Problems to be Solved by the Invention

However, the following problems exist in the above-mentioned conventional ceramic electronic component. In other words, moisture during plating may seep into the voids of the external electrodes, and there is a problem that "bursts" occur when the ceramic electronic component is mounted by the moisture. This "burst" is a phenomenon that when the external electrode is heated at the time of mounting, the moisture which permeated into the space | gap of an external electrode evaporates and a solder bursts by the vapor pressure. When bursting occurs in this way, there is a defect that the broken solder is attached to ceramic electronic parts, other mounting parts, and printed wirings, resulting in short defects or the like.

This invention is made | formed in order to solve the above-mentioned subject, and an object of this invention is to provide the electrode paste, ceramic electronic component, and its manufacturing method which can suppress generation | occurrence | production of a burst.

Means to solve the problem

The method for manufacturing a ceramic electronic component according to the present invention is applied to the manufacture of a ceramic electronic component having a ceramic element in which a dielectric layer and an electrode layer are alternately stacked, and an external electrode formed on an end surface on which the electrode layer of the ceramic element is exposed. Applying an external electrode paste comprising a first powder composed of Cu and a second powder composed of a metal having a higher ionization tendency than Cu, and firing a ceramic device to which the external electrode paste is applied. And a weight ratio of the second powder to the first powder is 0.5 to 10% by weight, and the average particle diameter of the second powder is 0.2 to 10 µm.

In the manufacturing method of this ceramic electronic component, in addition to the 1st powder which consists of Cu, the external electrode paste contains the 2nd powder which consists of metal which is higher in ionization tendency than Cu. The inventors and the like have made a ceramic electronic component by applying an external electrode paste containing only a predetermined amount of a second powder having a particle size of a predetermined range, which is made of a metal having a higher ionization tendency than Cu, to produce a ceramic electronic component. It has been newly discovered that the occurrence of bursting can be significantly suppressed while the external electrode of the ceramic electronic component maintains sufficient strength.

Moreover, it is preferable that the metal which is higher in ionization tendency than Cu which comprises a 2nd powder is at least 1 sort (s) of metal of nickel, cobalt, and titanium.

The ceramic electronic component according to the present invention comprises a first powder composed of Cu and a second powder composed of a metal having a higher ionization tendency than Cu, on the end surface of the ceramic element in which the dielectric layer and the electrode layer are alternately stacked, with the electrode layer exposed. A ceramic electronic component obtained by firing a ceramic element coated with an external electrode paste, wherein the external electrode paste is applied, wherein the weight ratio of the second powder to the first powder is 0.5 to 10% by weight, and the second powder The average particle diameter is characterized in that 0.2 to 10㎛.

The external electrode paste used in producing this ceramic electronic component includes, in addition to the first powder composed of Cu, a second powder composed of a metal having a higher ionization tendency than Cu. The inventors have studied diligently and in the ceramic electronic component produced by applying an external electrode paste containing only a predetermined amount of a second powder having a particle size of a predetermined range made of a metal having a higher ionization tendency than Cu to a ceramic element, It was newly discovered that the occurrence of bursting was significantly suppressed while the electrode maintained sufficient strength.

Moreover, it is preferable that the metal which is higher in ionization tendency than Cu which comprises a 2nd powder is at least 1 sort (s) of metal of nickel, cobalt, and titanium.

The electrode paste which concerns on this invention is equipped with the binder, the 1st powder which is less than 20 micrometers of average particle diameters which consist of Cu, and the 2nd powder which consists of a metal with a higher ionization tendency than Cu, The 2nd to 1st powder The weight ratio of the powder is 0.5 to 10% by weight, and the average particle diameter of the second powder is 0.2 to 10 µm.

This electrode paste contains, in addition to the first powder composed of Cu, a second powder composed of a metal having a higher ionization tendency than Cu. The inventors, after earnestly researching, use such an electrode paste as, for example, an external electrode paste for use in the manufacture of ceramic electronic components, thereby producing an external electrode having sufficient strength and significantly suppressing the occurrence of bursting. I found something new.

Moreover, it is preferable that the metal which is higher in ionization tendency than Cu which comprises a 2nd powder is at least 1 sort (s) of metal of nickel, cobalt, and titanium.

Effects of the Invention

According to the present invention, there is provided an electrode paste, a ceramic electronic component, and a manufacturing method thereof, which can suppress the occurrence of bursting.

1 is a schematic cross-sectional view of a ceramic capacitor according to an embodiment of the present invention.

2 is a partially enlarged view showing a printing pattern of a green sheet.

3 is a diagram illustrating a procedure of manufacturing a ceramic capacitor.

4A is a cross-sectional photograph of an external electrode obtained by firing an electrode paste to which nickel powder is not added, and FIG. 4B is a cross-sectional photograph of an external electrode obtained by firing an electrode paste to which nickel powder is added.

5 is a table showing the experimental results according to the embodiment of the present invention.

6 is a schematic plan view showing a substrate used for strength measurement according to an embodiment.

7 is a view showing a strength measurement method in the embodiment.

Brief description of symbols for the main parts of the drawings

10: ceramic capacitor

11: surface layer

12: dielectric layer

14: internal electrode layer

16: capacitor body

18: external electrode

18a: external electrode surface

20, 21: green sheet

20a: surface

22: internal electrode paste

26: laminate

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, with reference to an accompanying drawing, the aspect considered to be the best in implementing the electrode paste which concerns on this invention, a ceramic electronic component, and its manufacturing method is demonstrated in detail. In addition, the same code | symbol is attached | subjected about the same or equivalent element, and the description is abbreviate | omitted when description is duplicated.

1, the schematic sectional drawing of the ceramic capacitor which concerns on embodiment of this invention is shown. As shown in FIG. 1, the ceramic capacitor 10, which is a kind of ceramic electronic component, includes two outer surface layers 11 as outermost layers, about 300 dielectric layers 12 between the surface layers 11, and A six-sided condenser element 16 (ceramic element) having an internal electrode layer 14 interposed between each of the dielectric layers 12 disposed above and below is provided. That is, the capacitor body 16 has a laminated structure of about 600 layers, and the dielectric layer 12 and the internal electrode layer 14 are alternately stacked. In addition, it extends in the thickness direction of the capacitor body 16 among the end surfaces of the capacitor body 16, and each of the pair of end faces 16a and 16b facing each other covers the entire area of the end faces 16a and 16b. A pair of external electrodes 18 and 18 are provided.

In addition, the internal electrode layers 14 disposed above and below are electrically insulated from each other by the dielectric layer 12, and are connected to the external electrodes 18 which are different from each other. Therefore, when a predetermined voltage is applied between the pair of external electrodes 18 and 18, electric charges are accumulated between the internal electrode layers 14 facing up and down. In addition, the capacitance of the ceramic capacitor 10 is proportional to the size of the opposing area of the internal electrode layer 14 facing up and down.

The surface layer 11 and the dielectric layer 12 are both layers containing BaTiO ₃ as a main component, the thickness of each surface layer 11 is about 50 μm, and the thickness of each dielectric layer 12 is about 1 to 4 μm. These surface layers 11 and dielectric layers 12 are formed by firing a green sheet (ceramic molded body) described later. In addition, the internal electrode layer 14 is a metal layer containing Ni as a main component, and the thickness is about 1 micrometer. Each external electrode 18 is a porous body mainly composed of Cu having high conductivity among metals, and the arithmetic mean roughness of the surface 18a is about 1 µm.

Hereinafter, the method of manufacturing the ceramic capacitor 10 mentioned above is demonstrated, referring FIG. 2 and FIG. 2 is a partially enlarged view showing a printing pattern of a green sheet, and FIG. 3 is a diagram showing a procedure for manufacturing a ceramic capacitor.

In manufacturing the ceramic capacitor 10, as shown in FIG. 2, first, the dielectric green sheet 20 of the BaTiO ₃ system is prepared. The green sheet 20 is a sheet-shaped dielectric paste prepared by mixing BaTiO ₃ powder and an organic binder into a slurry. Moreover, two sheets of thickness greener than the green sheet 20 and used as the surface layer 11 are prepared.

And the internal electrode paste 22 of a predetermined pattern is apply | coated and dried to the surface 20a of the green sheet 20 by the screen printing method. That is, the internal electrode paste 22 is apply | coated to the area | region other than the edge area of three sides of the rectangular area | region 24 corresponding to one capacitor | condenser of the green sheet surface 20a (refer FIG. 2). The internal electrode paste 22 is formed into a paste by dispersing nickel powder in an organic binder and an organic solvent. A well-known thing can be used for an organic binder, For example, a cellulose resin, an epoxy resin, an aryl resin, an acrylic resin, a phenol-formaldehyde resin, an unsaturated polyester resin, a polycarbonate resin, a polyamide resin, a polyimide resin, an alkyd Binders, such as resin and rosin ester, can be used. Moreover, a well-known thing can also be used for an organic solvent, For example, solvents, such as butyl carbitol, butyl carbitol acetate, telepin oil, (alpha)-terebinol, ethyl cellosolve, and butyl phthalate, can be used.

BaTiO ₃ powder is added to the internal electrode paste 22 as a common material. Since the BaTiO ₃ powder has the same BaTiO ₃ as the main component of the dielectric layer 12 (and the green sheet 20), the addition of the BaTiO ₃ powder to the internal electrode paste 22 causes the internal electrode paste 22 and the green sheet ( The difference between the shrinkage rate and the sintering start temperature between 20) is significantly alleviated.

Then, the green sheet 20 to which the internal electrode paste 22 is applied as described above is laminated on the green sheet 21 with the internal electrode paste 22 on (see FIG. 3A). In addition, about 300 green sheets 20 produced by the same manufacturing method are sequentially stacked so that the positions of the internal electrode pastes 22 alternately change (see FIG. 3B). Then, the green sheet 21 is coated on the laminated green sheet 20, and nothing is applied. The green sheet 21 is pressed from the lamination direction, and the adjacent green sheet 21, green sheet 20 and internal electrode paste 22 are pressed. ) To each other. In this way, the laminated body 26 by which the green sheet 20 and the internal electrode paste 22 were alternately laminated is produced.

The laminate 26 is cut into chips for each rectangular region 24 corresponding to one capacitor (see FIG. 3C). Thereafter, the chipped laminate 26 is fired at, for example, about 1200 ° C., so that the green sheet 21, the green sheet 20, and the internal electrode paste 22 are respectively the surface layer 11 and the dielectric layer 12 described above. ) And the internal electrode layer 14, and the laminate 26 is a capacitor body 16 in which the dielectric layer 12 and the internal electrode layer 14 are alternately stacked. In addition, surface polishing is performed by treating the capacitor body 16 in a barrel containing water and a polishing medium. This surface polishing may be performed at the stage of the laminate 26.

Finally, the external capacitor 18 is formed so as to cover the pair of end faces 16a and 16b facing each other, extending in the stacking direction, among the end faces of the capacitor body 16, thereby completing the ceramic capacitor 10. (See FIG. 3 (d)). Hereinafter, the formation method of the external electrode 18 is demonstrated concretely.

First, an electroconductive paste for external electrodes (external electrode paste) containing copper powder (first powder), nickel powder (second powder), and an organic binder is prepared. Here, the average particle diameter of nickel powder is 0.2 micrometer, and the weight ratio of nickel powder to copper powder is 2 weight%. Then, this external electrode paste is applied to the end faces 16a and 16b of the capacitor body 16. Thereafter, the capacitor body 16 coated with the external electrode paste is subjected to a heat treatment at 800 ° C. in a neutral atmosphere or a reducing atmosphere, and the external electrode paste is sintered to form the external electrode 18.

Thereafter, the surface 18a of the external electrode 18 is plated with copper, nickel, tin, or the like. By applying such plating treatment to the external electrode 18, the connection reliability and wettability of the solder and external electrode 18 used when mounting the ceramic capacitor 10 on the substrate are improved.

The ceramic capacitor 10 produced as mentioned above is demonstrated.

As described above, the external electrode paste contains nickel powder in addition to copper powder. The external electrode obtained by baking such an external electrode paste is demonstrated referring FIG. Fig. 4 is a cross-sectional photograph of an external electrode obtained by firing (a) an electrode paste to which nickel powder is not added, and (b) a cross-sectional photograph of an external electrode obtained by firing an electrode paste to which nickel powder is added. 4 shows that when nickel is not added to the external electrode paste (see FIG. 4A), very little voids are formed in the external electrode, and the slightly formed voids are surrounded by equivalent metal components and are almost sealed. On the other hand, when nickel is added to the external electrode paste (see FIG. 4B), many voids are formed in the external electrode to increase porosity, and the voids are hardly sealed. In other words, it is considered that by adding nickel to the electrode paste, a porous (porous) external electrode is formed.

The inventors have investigated whether or not the burst occurs with respect to the external electrode 18 having a high porosity, and it was found that the burst was significantly suppressed at this external electrode. It was also found that bursting was also suppressed even when a metal having a higher ionization tendency than copper, such as cobalt or titanium, was added to the external electrode paste instead of nickel. This is because when a metal having a higher ionization tendency than copper is added to the external electrode paste, excessive sintering of copper is suppressed by the metal, thereby forming an external electrode 18 having a porosity effective to suppress bursting. It is considered that moisture of plating applied to the external electrode 18 at the time of mounting becomes easy to evaporate in air.

Moreover, according to an experiment conducted by the inventors, it was found that the weight ratio of nickel powder to Cu powder and the average particle diameter of nickel powder are important factors in order to express the effect of suppressing the above-described bursting. That is, the weight ratio of the nickel powder to the Cu powder needs to be 0.5 to 10% by weight, and the average particle diameter of the nickel powder needs to be 0.2 to 10 µm. In addition, when the weight ratio of the nickel powder to the Cu powder is smaller than 0.5% by weight, or when the average particle diameter of the nickel powder is larger than 10 µm, copper sintering inhibition by nickel is not sufficiently performed, so that the porosity of the external electrode is reduced. do. On the other hand, when the weight ratio of nickel powder to Cu powder is larger than 10% by weight, or when the average particle diameter of nickel powder is smaller than 0.2 µm, copper sintering inhibition by nickel is excessively performed, and the porosity of the external electrode becomes excessively high. This adversely affects the strength of the external electrode.

Example

Hereinafter, the content of the present invention will be described in detail by way of examples.

First, the external electrode paste used in Example 1 is demonstrated. The external electrode paste used in the present embodiment is a mixture of Cu powder as a main component, Ni powder having a weight ratio of 2 wt% to Cu powder and an average particle diameter of 0.2 μm, an organic binder, a dispersant, an organic solvent, and the like, It is made into paste form by disperse | distributing to a ball mill or a roll mill. And the external electrode of the ceramic capacitor was formed using this external electrode paste. Baking of the Cu terminal electrode was made into 800 degreeC in neutral atmosphere or reducing atmosphere, and the ceramic capacitor which is a sample was obtained. And about this sample, the porosity, the porosity, the bursting defect, and the external electrode strength were investigated. In addition, 14 kinds of samples were prepared by changing the type of metal to be added, the weight ratio to the Cu powder, and the average particle diameter, and the porosity, the porosity, the defective defect, and the external electrode strength were examined for each sample (Fig. 5).

Here, the "Example 2" sample is a sample which changed the average particle diameter of Ni powder used for the "Example 1" sample to 2 micrometers. The "Example 3" sample is a sample which changed the average particle diameter of Ni powder used for the "Example 1" sample to 10 micrometers. The "Example 4" sample is a sample which changed the average particle diameter of Ni powder used for the "Example 1" sample to 2 micrometers, and changed the weight ratio with respect to Cu powder to 0.5 weight%. The "Example 5" sample is a sample which changed the average particle diameter of Ni powder used for the "Example 1" sample to 2 micrometers, and changed the weight ratio with respect to Cu powder to 1 weight%. "Example 6" A sample is a sample which changed the average particle diameter of Ni powder used for the "Example 1" sample to 2 micrometers, and changed the weight ratio with respect to Cu powder to 4 weight%. "Example 7" A sample is a sample which changed the average particle diameter of Ni powder used for the "Example 1" sample to 2 micrometers, and changed the weight ratio with respect to Cu powder to 10 weight%.

"Example 8" The sample is a sample using Co powder having an average particle diameter of 2 µm and a weight ratio to Cu powder of 2% by weight instead of the Ni powder used for the "Example 1" sample. The "Example 9" sample is a sample using a Ti powder having an average particle diameter of 2 µm and a weight ratio of 2% by weight to the Cu powder, instead of the Ni powder used for the "Example 1" sample.

In addition, the sample which did not add Ni powder was prepared as a "comparative example 1" sample for comparison. "Comparative Example 2" The sample is a sample in which the average particle diameter of the Ni powder used for the "Example 1" sample was changed to 0.05 µm and the weight ratio to the Cu powder was changed to 2% by weight. "Comparative Example 3" The sample is a sample in which the average particle diameter of the Ni powder used for the "Example 1" sample was changed to 20 µm and the weight ratio to the Cu powder was changed to 2% by weight. "Comparative Example 4" The sample is a sample in which the average particle diameter of the Ni powder used for the "Example 1" sample was changed to 2 µm and the weight ratio to the Cu powder was changed to 0.1 wt%. "Comparative Example 5" The sample was a sample in which the average particle diameter of the Ni powder used for the "Example 1" sample was changed to 2 µm and the weight ratio to the Cu powder was changed to 20% by weight.

Here, "pore degree" is an item which shows the degree to which there is a space in which nothing in the terminal electrode is filled, and it measured by cross-sectional observation by SEM. The "porosity" is a value calculated from the following formula (1) using the density (actual density) derived based on the volume and weight of the sintered sample of the terminal electrode and the theoretical density of the components of the terminal electrode. Is a numerical value.

α = (1-d _r / d _t ) 100

Is the porosity, d _r is the actual density, and d _t is the theoretical density.

6 is a schematic plan view showing a substrate used for measuring the strength used in the present example. That is, a pair of band-shaped copper foils 32A, 32B (1.0 mm wide) are arranged on a simulated mounting substrate (30; 100 mm × 40 mm) made of glass cloth base epoxy resin and arranged in one axial direction. It is formed, and the soldering resist film 34 is formed on this copper foil 32A, 32B. Moreover, the both ends 36a, 36b, 38a, 38b of each copper foil 32A, 32B are exposed. Then, a sample (not shown) is provided on the mounting substrate 30 so that the external electrodes are positioned on the opposing ends 36a and 38a of both copper foils 32A and 32B. Moreover, the space | interval distance (symbol a in drawing) of the both copper foils 32A and 32B, the installation width | variety (symbol b in drawing) of a sample, and the width | variety of the opposing ends 36a and 38a of both copper foils 32A and 32B are opposite. Reference numeral c in the drawings is standardized in JIS. For example, a sample of the C3225 type has a = 2.2 mm, b = 5.0 mm, and c = 2.9 mm.

On the other hand, the cream solder was apply | coated to the external electrode of the sample used for intensity | strength measurement by the metal mask (thickness: 0.25 mm). And the sample was mounted on the board | substrate 30 by the reflow soldering system (peak temperature: 240 degreeC). And using the press head 40 of the shape as shown in FIG. 7, the load was applied to the substantially center part of the sample 42 on the conditions of the displacement speed of 30 mm / min. And the sample which was not destroyed until the load of 5 N was applied was judged as good, and the sample which was broken was defective. In addition, destruction of a sample means the case where part or all of the external electrode 44 peeled from a sample main body, etc., for example.

As is apparent from the table of FIG. 5, in the "Example 1" to "Example 9" samples, both "defective failure" and "external electrode strength" showed good results. On the other hand, a burst failure occurred in the "Comparative Example 1" sample, the "Comparative Example 3" sample, and the "Comparative Example 4" sample, and the external electrode intensity met the reference value in the "Comparative Example 2" sample and the "Comparative Example 5" sample. I didn't let it. Moreover, the porosity of each of the "Example 2" sample and the "Example 6" sample was 34.06%, 38.85%. In addition, the porosity of "Comparative Example 1" was 25.98%. From these porosity data, it is thought that bursting is unlikely to occur in an external electrode having a porosity of about 34 to 39%.

This invention is not limited to the said embodiment, A various deformation | transformation is possible. For example, a ceramic electronic component is not limited to a ceramic capacitor, For example, various electronic components, such as a piezoelectric chip component and a chip varistor component, may be sufficient.

Claims (6)

It is applied to the manufacture of a ceramic electronic component having a ceramic device having a dielectric layer and an electrode layer alternately stacked, and an external electrode formed on an end surface of the ceramic layer exposed by the electrode layer, Applying an external electrode paste including a first powder composed of Cu and a second powder composed of a metal having a higher ionization tendency than Cu to the cross section of the ceramic element; Firing the ceramic element coated with the external electrode paste;  The weight ratio of the second powder to the first powder is 0.5 to 10% by weight, the average particle diameter of the second powder is 0.2 to 10㎛, the porosity of the external electrode is 34 to 39% of the ceramic electronic component Manufacturing method. The method of claim 1, A method of producing a ceramic electronic component, wherein the metal having a higher ionization tendency than the Cu constituting the second powder is one of nickel, cobalt or titanium.  An external electrode paste comprising a first powder composed of Cu and a second powder composed of a metal having a higher ionization tendency than Cu is applied to an end surface of the ceramic element in which a dielectric layer and an electrode layer are alternately laminated, and the electrode layer is exposed. A ceramic electronic component obtained by firing the ceramic element coated with the external electrode paste,  The weight ratio of the second powder to the first powder is 0.5 to 10% by weight, the average particle diameter of the second powder is 0.2 to 10㎛, the porosity of the external electrode is 34 to 39%. The method of claim 3, wherein A metal having a higher ionization tendency than the Cu constituting the second powder is one of nickel, cobalt or titanium, the ceramic electronic component. delete delete

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