JP7355182B2 - Manufacturing method for chip-type ceramic electronic components - Google Patents

Description

The present invention relates to a method for manufacturing a chip-type ceramic electronic component, and particularly to a method for forming external electrodes in a chip-type ceramic electronic component.

For example, JP-A-2011-26631 (Patent Document 1) describes a conductive paste containing copper powder that is applied to form external electrodes in chip-type ceramic electronic components such as multilayer ceramic capacitors. There is. In particular, in Patent Document 1, the problem is to provide oxidation resistance to copper powder, and in order to solve this problem, it is proposed to contain specific amounts of Bi and Mg inside the particles of copper powder. .

In order to reduce the external dimensions of a chip-type ceramic electronic component, one effective means is to reduce the thickness of the external electrode formed on the outer surface of the component body of the chip-type ceramic electronic component. In order to obtain an external electrode with a thin film and high density, i.e., fewer defects and fewer voids, by baking a conductive paste, it is necessary to atomize the copper powder and glass powder contained in the conductive paste. . For example, methods such as a liquid phase reduction method or a gas phase method (thermal plasma method) are known as methods for obtaining finely divided copper powder having a particle size of 1 μm or less.

On the other hand, if fine-grained copper powder with a particle size of 1 μm or less is used as the copper powder included in the conductive paste, gas is likely to be generated when the copper powder is sintered, which may cause problems with blisters on the external electrode. There is. Examples of gases that cause blisters include SO ₂ gas derived from sulfur contained as an impurity in copper powder, and CO ₂ gas derived from carbon contained in glass powder.

In order to suppress blister defects, it is considered effective to delay the start of sintering of fine copper powder. For example, if it is possible to delay the start of sintering by adding oxides such as ZrO ₂ or Al ₂ O ₃ to the copper powder as a sintering retarder, it is possible to secure a path for the gas generated during the degreasing process to escape. Therefore, blister failure can be suppressed.

Japanese Patent Application Publication No. 2011-26631

However, according to the above-mentioned blister suppression technology, quality problems such as deterioration of the contact performance of the external electrode with the internal electrode that is inside the component body of the chip-type ceramic electronic component and should be electrically connected to the external electrode occur. You may encounter issues with. That is, there is a trade-off relationship between suppressing blisters and ensuring contact performance between the external electrode and the internal electrode.

An object of the present invention is to provide a method for manufacturing a chip-type ceramic electronic component in which contact performance between external electrodes and internal electrodes is ensured .

This invention is
It is formed by laminating a plurality of ceramic layers, and a plurality of internal electrodes containing nickel are arranged along the lamination direction of the ceramic layers, with a ceramic layer interposed between adjacent internal electrodes. The main body of the part ,
an external electrode provided on the outer surface of the component body;
Equipped with
the internal electrode has an exposed end exposed to the outer surface of the component body;
The external electrode is electrically connected to the internal electrode at the exposed end.
The present invention is directed to a method for manufacturing chip-type ceramic electronic components.

The method for manufacturing a chip-type ceramic electronic component according to the present invention includes:
In order to form the above-mentioned external electrode, copper powder and glass powder are included, the copper powder has a particle size of 300 nm or less, a particle size/crystallite size of more than 1.0 and less than 3.8, and the copper powder and a step of applying a conductive paste to the outer surface of the component body, in which the volume ratio of the glass powder to the total volume of the glass powder is 35% by volume or less;
The conductive paste is fired to form a Ni--Cu alloy layer on the exposed end of the internal electrode in the component body and in the vicinity thereof , and in a region other than the region where the Ni--Cu alloy layer is formed, forming a glass layer in a region of the external electrode in contact with the component body, and forming the external electrode so that the thickness of the external electrode on the surface of the component body after firing is 30 μm or less;
It is characterized by including.

According to this invention, the Ni--Cu alloy layer formed in the external electrode at and near the exposed end of the internal electrode in the component body functions to electrically connect the plurality of internal electrodes to each other, and Contributes to improved contact performance between electrodes and internal electrodes. Furthermore, the Ni--Cu alloy layer also contributes to improving the moisture sealing properties of the external electrode.

Further, according to the present invention, the glass layer formed in the area other than the area where the Ni-Cu alloy layer is formed and in contact with the component body of the external electrode improves the adhesion performance of the external electrode to the component body. Contribute to improvement.

1 is a cross-sectional view schematically showing a part of a chip-type ceramic electronic component 1 obtained by carrying out a manufacturing method according to an embodiment of the present invention. 2 is a diagram showing a micrograph taken of an actual sample corresponding to the chip-type ceramic electronic component 1 shown in FIG. 1. FIG. FIG. 3 is a diagram for explaining a method of evaluating the adhesion performance of an external electrode 24. FIG.

First, a conductive paste used to form external electrodes in a chip-type ceramic electronic component obtained by carrying out a manufacturing method according to an embodiment of the present invention will be described. The conductive paste contains copper powder and glass powder, and further contains appropriate amounts of resin and solvent to provide paste properties.

The copper powder contained in the conductive paste is a fine powder with a particle size of 300 nm or less. The particle size was determined by photographing the surface of the copper powder using a scanning electron microscope (SEM) and using image analysis software. Further, the crystallinity of the copper powder is high, and the particle size/crystallite size of the copper powder is 2.0 or less. Here, the crystallite diameter is determined by measurement using an X-ray diffraction (XRD) method. Note that since the crystallite diameter is never larger than the particle diameter, the ratio of particle diameter/crystallite diameter is a value exceeding 1.0.

The above particle diameter/crystallite diameter is preferably 1.1 or more and 2.0 or less. Thereby, blister defects can be made less likely to occur. Moreover, it is preferable that the crystallite diameter of the copper powder is 50 nm or more. This also contributes to further enhancing the effect of suppressing blister defects.

Preferably, the copper powder consists of spherical powder particles. According to this, the glass ratio in the dry coating film of the conductive paste can be reduced, so the glass content can be reduced, and as a result, the external electrode can be made denser. Therefore, even in ultra-small chip-type ceramic electronic components with planar dimensions of 0.2 mm x 0.1 mm, for example, the external Good conductivity can be achieved between the electrode and the internal electrode.

Note that if the particle size of the copper powder is made smaller, such as 100 nm, rather than 300 nm, the conductivity between the external electrode and the internal electrode described above will be better. The fixing performance of the external electrode can be further improved.

Preferably, the copper powder is produced by a vapor phase method. According to the vapor phase method, as described above, copper powder having a particle size of 300 nm or less and a particle size/crystallite size of 2.0 or less can be easily produced. Further, according to the vapor phase method, the inside of the powder particles of the copper powder can be made to contain no or almost no impurities. In particular, when chlorine is included as an impurity, the amount of chlorine ions can be set to 0.01% by mass or less. Note that this chlorine ion amount is a value measured by combustion ion chromatography. Further, when sulfur is contained as an impurity, the amount of sulfur can be limited to 0.002% by mass or less. Note that this sulfur content is a value measured by high frequency inductively coupled plasma emission spectroscopy (ICP-AES).

On the other hand, the volume ratio of the glass powder to the total volume of inorganic components in the conductive paste, that is, the total volume of the copper powder and the glass powder, is 35 volume% or less, preferably 10 volume% or more and 25 volume% or less. It is said that For example, if the volume ratio of the glass powder is set to the upper limit of 35% by volume, there is no problem if the particle size of the copper powder is, for example, 100 nm or less, but if the particle size of the copper powder is, for example, 300 nm, the internal electrode The contact performance of the external electrode may deteriorate. Therefore, as described above, the volume ratio of the glass powder is preferably 10% by volume or more and 25% by volume or less.

Preferably, the particle size of the glass powder is selected to be 1.0 μm or less. Similarly to the case of copper powder, the particle size of the glass powder was determined by photographing the surface of the glass powder using an SEM and using image analysis software.

Further, the glass powder is preferably made of B--Si glass. In this case, the B--Si glass may contain Ba or Sr as an additive element.

As described above, the conductive paste further contains appropriate amounts of resin and solvent. As the resin, known resins such as acrylic resin, ethyl cellulose resin, and butyral resin are used. As the solvent, preferably an alcohol solvent such as terpineol is used. A dispersant may be added to the solvent.

FIG. 1 shows a cross-sectional view of a part of a chip-type ceramic electronic component 1 in which external electrodes 2 are formed using the above-mentioned conductive paste. In FIG. 1, a chip-type ceramic electronic component 1 is schematically illustrated. Therefore, the form of each element and the dimensional ratio between each element shown in FIG. 1 may differ from the actual one (see FIG. 2).

The chip-type ceramic electronic component 1 constitutes, for example, a multilayer ceramic capacitor, and includes a component body 4 formed by laminating a plurality of ceramic layers 3. The component body 4 has a first main surface 5 and a second main surface 6 facing each other, a first end surface 7 connecting them, and a second end surface 7 facing the first end surface 7 (not shown). Although not shown, it further has a first side surface and a second side surface that extend parallel to the paper surface of FIG. 1 and are opposed to each other.

Inside the component body 4, a plurality of first internal electrodes 9 and a plurality of second internal electrodes 10 are arranged along the stacking direction of the ceramic layers 3, with specific ceramic layers 3 interposed between adjacent ones. arranged alternately. The first internal electrode 9 is drawn out to the illustrated first end surface 7 . On the other hand, the second internal electrode 10 is extended to a second end surface (not shown). Internal electrodes 9 and 10 contain nickel as a conductive component.

The illustrated external electrode, that is, the first external electrode 2 , is formed on the first end surface 7 of the component body 4 and is electrically connected to the first internal electrode 9 . Although not shown, a second external electrode formed to face the first external electrode 2 is formed on the second end surface of the component body 4 and is electrically connected to the second internal electrode 10. There is. The first external electrode 2 and the second external electrode have substantially the same configuration. Therefore, below, the configuration of the first external electrode 2 will be explained in detail, and the explanation of the configuration of the second external electrode will be omitted.

The first external electrode 2 extends from the first end surface 7 to the adjacent first and second main surfaces 5 and 5 so that the thickness on the end surface 7 of the component body 4 after firing is 30 μm or less. 6 and a portion of each of the first and second side surfaces. In order to form the external electrode 2 in this form, first, the above-mentioned conductive paste is applied to the outer surface of the component body 4, and the conductive paste is fired to form the internal electrodes 9 and 2 on the component body 4. A step of forming a Ni--Cu alloy layer on the exposed end of 10 and its vicinity is performed. More specifically, a conductive paste film is formed by applying the above-described conductive paste to a predetermined portion of the component body 4 by a dipping method or the like, and this conductive paste film is fired. In the firing step, a temperature of 750°C or lower is applied, for example 700°C.

The above-described firing step includes a step of forming the Ni--Cu alloy layer 11 on the exposed ends of the internal electrodes 9 and 10 in the component body 4 and in the vicinity thereof. More specifically, when the above-described firing step is performed, the exposed end of the first internal electrode 9 on the first end face 7 of the conductive paste film and the vicinity thereof are exposed to the nickel contained in the internal electrode 9. Copper contained in the conductive paste is mutually diffused, and a Ni--Cu alloy layer 11 is formed in the external electrode 2. It is preferable that the Ni--Cu alloy layer 11 has no voids and substantially no glass. The Ni-Cu alloy layer 11 functions to electrically connect the plurality of first internal electrodes 9 to each other, and contributes to improving the contact performance between the external electrode 2 and the internal electrode 9. It also contributes to improving moisture sealing properties.

In addition, the above-mentioned firing process causes the glass powder contained in the conductive paste to be removed from the area other than the area where the Ni--Cu alloy layer 11 is formed and which is in contact with the component body 4 of the external electrode 2. It includes a step of forming a glass layer 12. As shown in FIG. 1, the glass layer 12 is preferably a continuous layer, but may be partially interrupted. The glass layer 12 contributes to improving the adhesion performance of the external electrode 2 to the component body 4.
Next, after forming the external electrode 2, a step of forming a plating film made of Sn, for example, on the external electrode 2 may be performed.

FIG. 2 shows a micrograph taken of an actual sample corresponding to the chip-type ceramic electronic component 1 shown in FIG. In FIG. 2, portions corresponding to the external electrode 2 and component body 4 shown in FIG. 1 are photographed. Although not particularly shown with lead lines, it can be seen in FIG. 2 that the first and second internal electrodes 9 and 10 are present in the component body 4. In the micrograph of FIG. 2, the dark streaks or spots in the external electrode 2 are due to the presence of glass.

A Ni--Cu alloy layer 11 is formed in the external electrode 2 at the exposed end of the first internal electrode 9 in the component body 4 and in the vicinity thereof . It is recognized that there are no voids in the Ni--Cu alloy layer 11, and that almost no glass is present. Furthermore, in an area other than the area where the Ni--Cu alloy layer 11 is formed and which is in contact with the component body 4 of the external electrode 2, a glass layer 12 extending in a stripe shape is formed.

Furthermore, it should be noted that no blister failure can be confirmed in the external electrode 2 of the chip-type ceramic electronic component 1 shown in FIG.

[Experiment example]
Next, experimental examples conducted using the conductive paste disclosed in this specification will be described.

The copper powder contained in the conductive paste is manufactured by a vapor phase method and is made of spherical powder particles having the specified particle size and crystallite size shown in the table below. Obtained from a vendor. Regarding the particle size of the copper powder, the surface of the copper powder was photographed using a SEM, and an average value D50 of 500 particle sizes was determined using image analysis software, and this was taken as the particle size. Regarding the crystallite diameter, crystallinity was measured using an X-ray diffractometer "D8 Advance" manufactured by Bruker, and the crystallite diameter was calculated from this measured value using dedicated software "TOPAS" manufactured by Bruker.

The glass powder contained in the conductive paste had a particle size of 1.0 μm or less and was made of B-Si-Ba glass.

A conductive paste was obtained by adding and mixing appropriate amounts of acrylic resin and terpineol to the above-mentioned copper powder and glass powder.

Further, the conductive paste was evaluated in terms of "blister", "contact performance", and "adhesion performance" as shown in the table below.

"Blister" is an evaluation of the occurrence of blister failure. More specifically, a conductive paste was applied to both ends of a component body with planar dimensions of 0.6 mm x 0.3 mm by a dipping method, and baked at a temperature of 720° C. to form external electrodes. Here, the thickness of the external electrode after firing on the end face of the component body was set to 30 μm or 50 μm, as described later. The appearance of 100 parts was observed, and if even one part had a blister defect, it was determined to be defective and marked with an "x" in the table below.

"Contact performance" is an evaluation of the contact performance between the external electrode and the internal electrode. More specifically, a conductive paste is applied to both ends of a component body with planar dimensions of 0.2 mm x 0.1 mm by a dipping method, and is baked at a temperature of 720°C to form external electrodes. A sample of a multilayer ceramic capacitor with a capacitance of 10 nF was obtained. Next, a temperature of 150° C. was applied to the sample multilayer ceramic capacitor for 1 hour, and then the initial capacity was measured after another 24 hours had elapsed. Next, the sample multilayer ceramic capacitor was charged for 5 seconds with an applied voltage of 12.6 V, which is twice the rated voltage, and then placed on a metal container to discharge the electrons accumulated inside the capacitor under 0 ohms. Thereafter, a temperature of 150° C. was again applied to the sample multilayer ceramic capacitor for 1 hour, and after another 24 hours, the capacitance was measured. The number of samples out of 20 whose capacity decreased by 5% or more compared to the above-mentioned initial capacity was counted. In the table below, if this number is 2 or more, it is indicated as "x", if it is 1, it is indicated as "△", and if it is 0, it is indicated as "○".

"Adhesion performance" is an evaluation of the adhesion performance of the external electrode to the component body. More specifically, a conductive paste is applied to both ends of a component body with planar dimensions of 0.2 mm x 0.1 mm by a dipping method, baked at a temperature of 720°C to form external electrodes, and then External electrodes were subjected to Sn plating to produce a multilayer ceramic capacitor as a sample. Next, as shown in FIG. 3, the component body 23 of the multilayer ceramic capacitor 22 is placed on the substrate 21 in an upright state, and the multilayer ceramic capacitor 22 is assembled by applying solder 25 to the lower external electrode 24. It was fixed to the substrate 21. In this state, the upper external electrode 27 was pushed horizontally as indicated by the arrow 26. The destruction mode caused by this horizontal push is
(1) Peeling at the interface between the substrate 21 and the solder 25,
(2) Peeling at the interface between the solder 25 and the plating film on the external electrode 24;
(3) Peeling at the interface between the external electrode 24 and the component body 23; and (4) cracking of the component body 23.
It was classified into four categories. If even one of the 10 samples encountered the failure mode (3), it was determined to be defective and marked with an "x" in the table below.

(Experiment example 1)
In Experimental Example 1, an external electrode was formed using a conductive paste containing copper powder having a "particle diameter", "crystallite diameter", and "particle diameter/crystallite diameter" as shown in Table 1. Further, the volume ratio of the glass powder to the total volume of the copper powder and the glass powder in the conductive paste was 25% by volume. In Experimental Example 1, the thickness of the external electrode after firing on the end surface of the component body was set to 30 μm.

In Table 1, in Samples 1, 2, and 4, the copper powder has a "particle size" of 300 nm or less, and a "particle size/crystallite size" of more than 1.0 and 3.8 or less. "Blister", "contact performance" and "adhesion performance" were evaluated as "○".

On the other hand, in sample 3, the "particle diameter/crystallite diameter" of the copper powder was 10.0, which exceeded 3.8, and the "blister" was evaluated as "x".

In addition, in sample 5, the "particle diameter/crystallite diameter" of the copper powder was 6.0, which exceeded 3.8, and the "blister" was evaluated as "x". In sample 5, the "particle size" of the copper powder is 300 nm, which is larger than 100 nm in sample 2, and the "adhesion performance" is evaluated as "x".

In addition, in sample 6, the "particle diameter" of the copper powder is 500 nm, which exceeds 300 nm, and the "particle diameter/crystallite diameter" is 5.0, which exceeds 3.8, so the "blister" and "contact performance" and "adhesion performance" were evaluated as "x".

In addition, in sample 7, the "particle diameter/crystallite diameter" of the copper powder exceeds 1.0 and is 3.8 or less, but since the "particle diameter" is 500 nm, which exceeds 300 nm, it is called "blister". "Contact performance" and "Adhesion performance" were evaluated as "x".

(Experiment example 2)
In Experimental Example 2, an external electrode was formed using a conductive paste containing copper powder having a "particle diameter", "crystallite diameter", and "particle diameter/crystallite diameter" as shown in Table 2. Further, the volume ratio of the glass powder to the total volume of the copper powder and the glass powder in the conductive paste was 25% by volume, as in Experimental Example 1. In Experimental Example 2, the thickness of the external electrode after firing on the end face of the component body was set to be 50 μm, which is thicker than in Experimental Example 1. It is assumed that the greater the thickness of the external electrode, the greater the risk of blister failure occurring.

In Table 2, all of Samples 11 to 18 have a "particle diameter" of 300 nm or less. Further, among samples 11 to 18, for samples 11 to 13 and 15 to 18, excluding sample 14, the copper powder has a "particle size/crystallite size" of more than 1.0 and 3.8 or less.

However, among samples 11 to 13 and 15 to 18, samples 11 and 17 were rated "x" for "blister". This is because the "particle size/crystallite size" of the copper powder is in the range of 1.1 or more and 2.0 or less for samples 12, 13, 15, 16, and 18, whereas for samples 11 and 17, This is considered to be because they are out of the range of 1.1 or more and 2.0 or less, and are 3.3 and 3.0, respectively.

For this reason, as the thickness of the external electrode becomes thicker, the risk of blister failure increases. It can be seen that it is desirable to narrow the range to 1.1 or more and 2.0 or less.

That is, in samples 12, 13, 15, 16, and 18, in which the "particle size/crystallite size" of the copper powder was narrowed to a range of 1.1 or more and 2.0 or less, the thickness of the external electrode was as thick as 50 μm. Also, the evaluation of "Blister" is "○".
Note that the evaluation of "x" for "blister" in Experimental Example 2 is not so serious. This is because, as in Experimental Example 1, if the thickness of the external electrode after firing on the end face of the component body is reduced to 30 μm or less , the problem of the blister failure can be solved.

(Experiment example 3)
In Experimental Example 3, an external electrode was formed using a conductive paste containing copper powder having a "particle diameter", "crystallite diameter", and "particle diameter/crystallite diameter" as shown in Table 3. Further, in Experimental Example 3, as in Experimental Example 1, the thickness of the external electrode after firing on the end surface of the component body was set to 30 μm.

In Experimental Example 3, the volume ratio of glass powder to the total volume of copper powder and glass powder in the conductive paste was changed in the range of 5 to 35 volume %, as shown in "Glass ratio" in Table 3.

First, focusing on the "particle diameter" of the copper powder, samples 29 to 31 have a diameter of 500 nm, which exceeds 300 nm. Therefore, the evaluation of at least one of "contact performance" and "adhesion performance" is "x".

On the other hand, in samples 21 to 28, the copper powder had a "particle size" of 300 nm or less, and a "particle size/crystallite size" of more than 1.0 and 3.8 or less, more specifically, 1.1. or more and 2.0 or less. Although not shown in Table 3, no blister failure occurred in these samples 21-28.

However, among samples 21 to 28, only samples 22 to 24, 26, and 27 were evaluated as ``○'' in both "contact performance" and "adhesion performance." Paying attention to the "glass ratio" in samples 22 to 24, 26 and 27, the "glass ratio" falls within the range of 10 to 25% by volume.

On the other hand, in samples 21 and 25, in which the "glass ratio" was less than 10 volume %, 5 volume % and 7 volume %, respectively, the "adhesion performance" was evaluated as "x". The reason why the evaluation of "adhesion performance" was "x" was because the "glass ratio" was relatively low, but even in sample 25, where the "glass ratio" was 7% by volume, which is higher than the 5% by volume of sample 21, " It is presumed that the reason why the "fixing performance" was evaluated as "x" was because the "particle diameter" of the copper powder was 300 nm, which was larger than the 100 nm of sample 21.

In addition, in sample 28 in which the "glass ratio" was 35% by volume, exceeding 25% by volume, the "contact performance" was evaluated as "△". On the other hand, in sample 24, which also has a "glass ratio" of 35% by volume, the "contact performance" is evaluated as "○". This is not a problem if the "particle size" of the copper powder is relatively small at 100 nm, as in sample 24, when the "glass ratio" is set to 35% by volume, which is relatively high. This indicates that there is a concern that the "contact performance" may deteriorate when the "particle diameter" of the "particle size" becomes relatively large, such as 300 nm. Looking at it from a different perspective, this shows that even if the "glass ratio" is relatively high at 35% by volume, good contact performance can be obtained if the "particle size" of the copper powder is made relatively small to 100 nm .

Above, we have mainly explained a multilayer ceramic capacitor as an example of a chip-type ceramic electronic component in which the conductive paste is applied to form external electrodes, but the conductive paste can also be used to form external electrodes of other chip-type ceramic electronic components. It can also be used for

1 Chip type ceramic electronic component 2 External electrode 4 Component body 9, 10 Internal electrode 11 Ni-Cu alloy layer 12 Glass layer

Claims (7)

It is formed by laminating a plurality of ceramic layers, and a plurality of internal electrodes containing nickel are arranged along the lamination direction of the ceramic layers, with the ceramic layer interposed between adjacent internal electrodes. There is a part body,
an external electrode provided on the outer surface of the component body;
Equipped with
The internal electrode has an exposed end exposed to the outer surface of the component body,
The external electrode is electrically connected to the internal electrode at the exposed end.
A method for manufacturing a chip-type ceramic electronic component, the method comprising:
In order to form the external electrode, a copper powder and a glass powder are included, and the copper powder has a particle size of 300 nm or less, a particle size/crystallite size of more than 1.0 and 3.8 or less, and Applying a conductive paste to the outer surface of the component body, in which the volume ratio of the glass powder to the total volume of the copper powder and the glass powder is 35% by volume or less;
The conductive paste is fired to form a Ni--Cu alloy layer at and near the exposed end of the internal electrode in the component body , and in an area other than the area where the Ni--Cu alloy layer is formed. A glass layer is formed in a region of the external electrode in contact with the component body, and the external electrode is formed so that the thickness of the external electrode after firing on the end surface of the component body is 30 μm or less. The process of
including,
A method for manufacturing chip-type ceramic electronic components. The method for manufacturing a chip-type ceramic electronic component according to claim 1, further comprising the step of forming a plating film on the external electrode. The method for manufacturing a chip-type ceramic electronic component according to claim 1 or 2, wherein the copper powder is composed of spherical powder particles. The method for manufacturing a chip-type ceramic electronic component according to any one of claims 1 to 3, wherein the volume ratio of the glass powder to the total volume of the copper powder and the glass powder is 10 volume % or more and 25 volume % or less. . The method for manufacturing a chip-type ceramic electronic component according to any one of claims 1 to 4, wherein the glass powder has a particle size of 1.0 μm or less. 6. The method for manufacturing a chip-type ceramic electronic component according to claim 1, wherein the glass powder is made of B--Si glass. 7. The method for manufacturing a chip-type ceramic electronic component according to claim 1, wherein the chip-type ceramic electronic component is a multilayer ceramic capacitor.

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