JP2002299145A - Ceramic laminate and method of manufacturing the same - Google Patents

Ceramic laminate and method of manufacturing the same

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Publication number
JP2002299145A
JP2002299145A JP2001097432A JP2001097432A JP2002299145A JP 2002299145 A JP2002299145 A JP 2002299145A JP 2001097432 A JP2001097432 A JP 2001097432A JP 2001097432 A JP2001097432 A JP 2001097432A JP 2002299145 A JP2002299145 A JP 2002299145A
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Japan
Prior art keywords
ceramic
insulator
layer
thickness
diameter
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Pending
Application number
JP2001097432A
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Japanese (ja)
Inventor
Seiichi Koizumi
成一 小泉
Original Assignee
Kyocera Corp
京セラ株式会社
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Application filed by Kyocera Corp, 京セラ株式会社 filed Critical Kyocera Corp
Priority to JP2001097432A priority Critical patent/JP2002299145A/en
Publication of JP2002299145A publication Critical patent/JP2002299145A/en
Pending legal-status Critical Current

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Abstract

(57) Abstract: The withstand voltage of a ceramic laminate can be improved by making the thickness of the insulator layer uniform and reducing the surface roughness (Ra) even when the insulator layer is thinned. Provided are a ceramic laminate and a method for producing the same. A plurality of insulator layers are laminated, an inner conductor is interposed between the insulator layers, and an average particle size of ceramic particles in the insulator layer on the side of the inner conductor is provided. The diameter is smaller than the average particle diameter of the ceramic particles at the center in the thickness direction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic laminate and a method of manufacturing the same, and more particularly, to a ceramic laminate in which an insulating layer and an internal conductor are thin and multilayered such as a wiring board and a multilayer ceramic capacitor, and a method of manufacturing the same. Things.

[0002]

2. Description of the Related Art In recent years, as electronic devices have become smaller and higher in density, wiring boards and ceramic capacitors having an internal conductor formed in a ceramic laminate have been required to be thinner and have higher dimensional accuracy. Ceramic capacitors are required to have a small size and a high capacity. For this reason, thinning and multilayering of insulating layers and internal conductors are being promoted.

[0003] In such a multilayer ceramic capacitor, the thickness variation and the surface roughness (Ra) of the insulator layer are affected by the capacitance, withstand voltage and insulation resistance of the multilayer ceramic capacitor as the thickness of the insulator layer is reduced. Because it greatly affects the thickness variation and surface roughness (Ra) of the insulator layer
The device is designed to reduce the noise.

[0004] As such a multilayer ceramic capacitor, one disclosed in, for example, JP-A-2000-277368 is known. In the multilayer ceramic capacitor disclosed in this publication, an insulator green sheet having a thickness of 5 μm or more has an average particle diameter represented by a 50% cumulative frequency distribution particle diameter (D50) measured by a particle size distribution meter such as a laser diffraction method. Is composed of a dielectric powder having a size of 1/5 or less of the effective layer thickness, and a 10% cumulative frequency distribution particle diameter (D10) measured by a particle size distribution analyzer of the same method or the like.
In a ratio of 50% cumulative frequency distribution particle diameter (D50) and 90% cumulative frequency distribution particle diameter (D90), D10 / D50
Is 0.5 or more and D90 / D50 is 1.45 or less.

[0005] By using such an insulator green sheet, it is possible to suppress the occurrence of defects such as voids and pores in the insulator layer and to reduce structural defects such as shorts and cracks and to increase reliability. A multilayer ceramic capacitor can be obtained.

[0006]

However, in the multilayer ceramic capacitor disclosed in JP-A-2000-277368, the case where the thickness of the insulator green sheet is 5 μm or more is described. The average particle size of the ceramic particles constituting the body green sheet is 0.69 μm or more in terms of a 50% cumulative frequency distribution particle size (D50). In such an insulator green sheet, a large number of ceramic powders having a large average particle diameter exist near the surface, and the surface roughness (Ra) of the insulator green sheet increases. There is a problem that the particles easily penetrate between the particles, and local thickness variation of the internal conductor and thickness variation of the insulator layer easily occur.

Further, in order to cope with recent increase in size and capacity,
When the thickness of the insulator layer is reduced to 3 μm or less, there is a problem that the influence of the penetration of the internal conductor into the insulator layer is further increased, and the dielectric breakdown voltage of the multilayer ceramic capacitor is significantly reduced.

Therefore, according to the present invention, even when the thickness of the insulator layer is reduced, the thickness of the insulator layer is made uniform and the surface roughness (R) is reduced.
It is an object of the present invention to provide a ceramic laminate and a method for producing the same which can improve the dielectric breakdown voltage by reducing a).

[0009]

A ceramic laminate according to the present invention is formed by laminating a plurality of insulator layers, an internal conductor is interposed between the insulator layers, and the internal conductor in the insulator layer is provided. The average particle size of the ceramic particles on the side is smaller than the average particle size of the ceramic particles at the center in the thickness direction.

The average particle size of the ceramic particles on the inner conductor side in the insulator layer is 0.3 μm or less, and the average particle size of the ceramic particles at the center in the thickness direction is 0.3 μm.
It is desirable that this is the case.

It is desirable that the ceramic particles on the inner conductor side and the ceramic particles at the center in the thickness direction in the insulator layer have the same composition.

Further, in the ceramic laminate of the present invention, the thickness of the insulator layer is desirably 3 μm or less.

In such a ceramic laminate, a ceramic slurry containing a large-diameter ceramic powder is applied on a carrier film, and a ceramic slurry containing a small-diameter ceramic powder is applied on the surface thereof to form an insulator green sheet. Forming an internal conductor pattern on a part of the surface of the insulator green sheet, and peeling the carrier film; and laminating and forming a plurality of the insulator green sheets on which the internal conductor pattern is formed. It can be produced by a step of producing a body and a step of firing the laminated molded body.

According to such a configuration, the inner conductor side in the insulator layer is formed of ceramic particles having a diameter smaller than that of the ceramic particles constituting the central portion in the thickness direction of the insulator layer, so that the surface of the insulator layer is formed. The roughness (Ra) can be reduced, the variation in thickness can be reduced, and the dielectric breakdown voltage of the insulator layer can be increased.

In other words, according to the present invention, the surface of the insulator green sheet becomes denser, so that the metal powder constituting the internal conductor pattern is prevented from entering the inside of the insulator green sheet, so that a short-circuit failure can be prevented. Can be eliminated.

Further, since the surface of the insulator green sheet is dense as described above, the internal conductor pattern can be formed uniformly, so that a decrease in the effective area of the internal conductor can be suppressed. The capacitance of the capacitor can be increased.

Further, in the above method, a ceramic slurry containing a small-diameter ceramic powder is applied on a carrier film, a ceramic slurry containing a large-diameter ceramic powder is applied on the surface thereof, and the small-diameter ceramic powder is further applied to the surface. By coating the ceramic slurry containing it to produce an insulator green sheet, both sides in the thickness direction of the insulator layer are composed of small-diameter ceramic particles. In addition to increasing the bonding strength between the insulator layers stacked one above the other, the mismatch in the firing shrinkage between the metal film of the internal conductor and the insulator layer, which generally has a high firing shrinkage, can be reduced, and delamination and cracks can be suppressed. .

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (Structure) The ceramic laminate of the present invention is applied to, for example, a multilayer ceramic capacitor as shown in FIG.

This ceramic laminate is formed by forming external electrodes 3 on both ends of a laminate body 1. On the surface of the external electrode 3, for example, a Ni plating layer 5, Sn
A plating layer or a Sn—Pb alloy plating layer 7 is formed.

The laminated body 1 includes an insulator layer 9 and an inner conductor 1.
1 are alternately laminated, and an insulating layer 13 made of the same material as the insulator layer 9 is formed on both surfaces in the laminating direction.

The insulator layer 9 constituting the laminate body 1 is made of a sheet-like ceramic sintered body.
It is composed of an insulator porcelain formed by firing an insulator green sheet containing BaTiO 3 as a main component.

On the other hand, the internal conductor 11 is made of a metal film obtained by sintering a conductive paste film. As the conductive paste, for example, a base metal such as Ni, Co, Cu or the like is used. Further, the internal conductor 11 is a substantially rectangular conductor film containing a base metal as a main component as described above,
The inner conductors 11 of the third layer, the fifth layer,.
One end thereof is exposed at one end surface of the multilayer body 1, and the inner conductors 1 of the second, fourth, sixth,...
1 has one end exposed to the other end surface of the multilayer body 1. Note that the external electrode 3 and the internal conductor 11 need not necessarily be made of the same material.

As shown in the enlarged view of FIG. 2, the insulator layer 9 of the present invention has a large particle layer 17 formed of ceramic particles having a large average particle diameter (ceramic large particles 15) at the center in the thickness direction. And the inner conductor 1 on both sides
A small particle layer 21 made of ceramic particles (ceramic small particles 19) having a small average particle size is formed on one side (the side on which the internal conductor is formed) and on the opposite side (the side on which the internal conductor is not formed). Is what you do. In addition, this small particle layer 2
1 may be one side of the insulator layer 9.

That is, it is important that a plurality of layers made of ceramic particles having different average particle sizes are formed in the thickness direction of the insulator layer 9.

The average particle size of the small ceramic particles 19 on the side of the internal conductor 11 is 0.3 μm or less, while the average particle size of the large ceramic particles 15 in the center of the insulator layer 9 in the thickness direction is 0.3 μm. It is desirable that this is the case.

The surface roughness (Ra) of the insulator layer 9 is as follows:
The thickness is desirably 100 nm or less from the viewpoint of preventing intrusion of the metal powder to be the inner conductor 11. In particular, from 50 to 100 because the bonding of the inner conductor 11 is enhanced.
nm is desirable.

For example, in the case of a multilayer ceramic capacitor having 100 or more layers, the average particle diameter of the small ceramic particles 19 constituting the small particle layer 21 is 0 because high smoothness is required. It is desirably 0.05 to 0.3 μm.

On the other hand, the average particle diameter of the large ceramic particles 15 constituting the large particle layer 17 at the center in the thickness direction of the insulator layer 9 is such that the relative dielectric constant and insulation resistance are high even if the insulator layer 9 is made thin. It is desirable that the thickness be 0.3 to 0.8 μm for the reason of maintaining.

In order to promote uniform sintering of the insulator layer 9 and to stabilize the dielectric and insulating properties of the insulator layer 9, the ceramic small particles 19 of the small particle layer 21 and the large particle layer The composition of the 17 large ceramic particles 15 is desirably the same.

Further, the thickness of the insulator layer 9 constituting the ceramic laminate of the present invention is desirably 3 μm or less for the reason that the thickness of the ceramic laminate is reduced to a small number of layers in order to increase the size and the capacity of the ceramic laminate. The thickness of the insulator layer 9 is desirably 1.5 to 3 μm for reasons of insulation.

[0031] Then, the thickness ratio of the small particle layer 21 to the thickness of the insulating layer 9, when the thickness of the insulator layer 9 and t 1, the thickness of the small particle layer 21 and t 2, t 2 / t 1 > 0.1 and t 2 <0.5 μm, the small particle layer 2 of the present invention
1 is suitably applied, furthermore, in order to increase the dielectric constant and insulation resistance of the insulator layer 9, the thickness ratio t 2 / t 1 is
Desirably, it is 0.1 to 0.3.

On the other hand, the thickness of the inner conductor 11 is desirably 2 μm or less. In order to reduce the amount of metal contained in the inner conductor 11 and to secure a sufficient effective area, the thickness of the inner conductor 11 is preferably 0.5 to 1 μm. Desirably, it is 5 μm.

That is, in the case of a multilayer ceramic capacitor having a thickness of the insulating layer 9 of 3 μm or less and the internal conductor 11 of 2 μm or less, for example, a multilayer ceramic capacitor having 100 or more layers, the internal conductor 1
The average particle diameter of the large ceramic particles 15 constituting the insulator layer 9 is 0.3 to 0.8 μm because the firing shrinkage difference between the ceramic layer 1 and the insulator layer 9 is reduced. The average particle size of the ceramic small particles 19 of the small particle layer 21 is 0.05 to 0.3 μm due to high packing of the particles, sinterability of the porcelain, and electrical and mechanical effects on the multilayer ceramic capacitor.
Is preferred. At this time, no structural defect such as a crack is observed with respect to the thermal shock resistance.

The number of layers of the ceramic laminated body of the present invention is such that even if the insulating layer 9 constituting the ceramic laminated body is formed into a thin multilayer, the penetration of the internal conductor 11 on the insulating layer 9 is prevented. Since the short circuit can be prevented and the delamination and cracks can be suppressed without any problem, the number of stacked ceramic layers is desirably 100 or more in order to increase the size and the capacity of the ceramic laminate.

(Manufacturing Method) Next, a manufacturing method of the ceramic laminate of the present invention, for example, a multilayer ceramic capacitor will be described with reference to FIG.

(A) First, a ceramic slurry containing a small-diameter ceramic powder is applied on a carrier film in advance to form a layer made of a small-diameter ceramic powder having a thickness of 0.3 to 1.5 μm (small-diameter particle sheet 25 (1)). Layer)) is formed.

(B) A ceramic slurry containing a large-diameter ceramic powder is applied to the surface layer to a thickness of 1.5 to 4 μm.
Layer composed of large-diameter ceramic powder (large-diameter particle sheet 26)
(2nd layer)) is formed.

(C) Further, a ceramic slurry containing a small-diameter ceramic powder is applied again to the upper layer, and a 0.3-1.5 μm-thick small-diameter particle sheet 25 (first layer)
To form an insulator green sheet 27 having a three-layer structure.

The three-layered insulator green sheet 27
Then, the average particle size of the ceramic small particles 19 constituting the third-layer small-diameter particle sheet 25 to which the internal conductor paste is applied is set to prevent the metal powder to be the internal conductor 11 from entering the inside of the insulator green sheet 27. Large particle sheet 26
It is preferable that the average particle size of the ceramic small particles 19 constituting the first layer of small-diameter particle sheet 25 formed on the opposite surface is smaller than the average particle size.

When the small-diameter particle sheet 25 is formed on one side of the large-diameter particle sheet 26 (not shown), a ceramic slurry containing a large-diameter ceramic powder is formed on a carrier film by slip casting. To form a large-diameter particle sheet 26 having a thickness of 1.5 to 4 μm,
A small-diameter particle sheet 2 having a thickness of 0.3 to 1.5 μm
5 (first layer) is formed.

Specific examples of the slip casting method for forming the insulator green sheet 27 include a lifting method,
A doctor blade method, a reverse roll coater method, a gravure coater method, a screen printing method, a gravure printing method, and a die coater method can be used.

The two-layer and three-layer insulator green sheets 27 can be formed continuously, for example, by arranging a plurality of doctor blades adjacent to each other in the molding direction.

As described above, the surface roughness (Ra) of the insulator green sheet 27 in which the small-diameter particle sheet 25 is formed on the surface of the large-diameter particle sheet 26 is as follows. Sheet 27 (Ra> 200)
nm), which is 100 nm or less.

As the insulator material, specifically, BaT
Ceramic powders such as iO 3 —MnO—MgO—Y 2 O 3 can be used because they have reduction resistance. Further, glass powder may be added. In this case, after firing, there are BaTiO 3 particles in which MnO, MgO and Y 2 O 3 are dissolved.

The average particle size of the ceramic powder (large-diameter ceramic powder) used for the large-diameter particle sheet 26 of the insulator green sheet 27 is determined by the average value of the insulator green sheet 27.
0.8 μm or less is desirable for the reason of thinning, and 0.3-0.7 μm for the reason of high dielectric property and high insulation property.
μm is desirable.

On the other hand, the average particle size of the small-diameter ceramic powder for forming the small-diameter particle sheet 25 is desirably 0.3 μm or less, so that the firing shrinkage ratio between the insulator layer 9 and the internal conductor 11 can be easily controlled, and In particular, the average particle size is 0.05 to 0.2 because the mechanical strength is increased without growth.
μm is desirable.

Further, Ba, which is a main raw material of the ceramic powder,
TiOThreePowder synthesis methods include solid phase method and liquid phase method (using oxalate).
Method, etc.) and hydrothermal synthesis methods, of which the particle size
Hydrothermal synthesis is desired because of the narrow cloth and high crystallinity
Good. And BaTiO ThreeThe average specific surface area of the powder is
2.0-10mTwo/ G is preferred.

(D) Next, this insulator green sheet 2
On the surface of 7, an internal conductor pattern 29 is formed using a conductive paste by a known printing method such as a screen printing method, a gravure printing, or an offset printing method. The thickness is desirably 2 μm or less, particularly preferably 1 μm or less from the viewpoint of miniaturization and high reliability of the multilayer ceramic capacitor.

The conductive paste contains metal particles, an organic solvent composed of a mixture of an aliphatic hydrocarbon and a higher alcohol, and an organic binder composed of ethyl cellulose soluble in the organic solvent. .

As the metal particles contained in the conductive paste, base metal particles having an average particle size of 0.05 to 0.5 μm are used. As base metals, there are Ni, Co, Cu and alloys thereof. Ni is used because the firing temperature of the metal matches the firing temperature of general insulators and the cost is low.
Is desirable.

The average particle size of the base metal particles is desirably in the range of 0.1 to 0.5 μm in order to improve the dispersibility of the metal powder and prevent the metal from being enlarged during firing. The base metal preferably has an average particle size of 0.15 to 0.4 μm because a dense and smooth surface metal film is formed. Also,
It is desirable that the average particle diameter of the base metal particles be the same as the average particle diameter of the small-diameter ceramic powder used for the insulator layer in order to prevent metal particles from entering the small particle layer formed on the insulator layer.

In the conductive paste, it is preferable to use a fine ceramic powder as a solid component in addition to the metal powder in order to suppress the sinterability of the internal conductor pattern. The average particle size of the ceramic powder is 0.0
5 to 0.3 μm is desirable.

In the insulator green sheet 27 of the present invention,
Even when the internal conductor pattern 29 is formed as described above, since the small-diameter particle sheet 25 is formed on the upper surface of the large-diameter particle sheet 26 of the insulator green sheet 27, the insulator green sheet 27 is printed when the conductor paste is printed. The internal conductor pattern 29 can be formed without the metal powder of the internal conductor 11 penetrating into the inside. Thereafter, the insulator green sheet 27 to which the conductor paste is applied is peeled from the carrier film.

(E) Next, a plurality of insulator green sheets 27 to which the conductive paste is applied are laminated,
The first lamination is performed at 80 ° C. and a pressure of 0.1 to 10 MPa to form a temporary laminated molded body. At this time, the laminated insulator green sheets 27 are not completely adhered, and a gap is left for sufficient degassing at the next second lamination.

Next, the temporary laminated molded body was heated to a temperature of 90 to 13 ° C.
A second laminating press is performed at 0 ° C. and a pressure of 10 to 100 MPa to completely adhere to each other to obtain a laminated molded body.

Next, the laminated molded body is cut into a lattice to obtain a molded body of the laminated body 1. One end of an internal conductor pattern 29 to be the internal conductor 11 is alternately exposed at both end surfaces of the molded body.

The laminated body 1 is not limited to the above-described method, but may be a thinned insulator green sheet 27.
A method such as slurry dip or the like may be used as long as a molded body in which the molded body in which the internal conductor patterns 29 and the internal conductor patterns 29 are alternately laminated can be manufactured.

Next, after removing the molded body of the laminated body 1 at 250 to 300 ° C. in the air or at 500 to 800 ° C. in a low oxygen atmosphere having an oxygen partial pressure of 0.1 to 1 Pa, a non-oxidizing atmosphere is obtained. At 1200 to 1300 ° C. for 2 to 3 hours. Further, if desired, the oxygen partial pressure is 0.1 to 10 -4 P
5 to 15 at 900 to 1100 ° C under low oxygen partial pressure of about a
The laminated body 1 reduced by performing the time reoxidation treatment is oxidized, so that the laminated body 1 having high capacitance and insulating properties can be obtained.

Finally, a Cu paste is applied to each end face of the obtained laminated body 1, a Ni / Sn plating layer is applied, and the external electrodes 3 electrically connected to the internal conductor 11 are formed. A multilayer ceramic capacitor is manufactured.

(Function) As described above, by forming the inner conductor 11 side of the insulator layer 9 with ceramic powder having a diameter smaller than that of the ceramic particles constituting the central portion in the thickness direction of the insulator layer 9, 9 can be reduced in surface roughness (Ra) and thickness variation can be reduced.
Can increase the dielectric breakdown voltage.

Since the surface of the insulator green sheet 27 becomes denser, the metal powder constituting the internal conductor pattern 29 is prevented from entering the inside of the insulator green sheet 27, so that a short circuit defect can be eliminated. it can.

In the above embodiment, an example in which the present invention is applied to a multilayer ceramic capacitor has been described. However, the present invention can be applied to, for example, a ceramic substrate having an internal conductor.

[0063]

EXAMPLE A multilayer ceramic capacitor, which is one of the ceramic laminates, was manufactured as follows.

First, when forming an insulator green sheet having a two-layer structure, a ceramic slurry containing a large-diameter ceramic powder is applied on a carrier film by a slip casting method, and a thickness of 2 to 3 μm is formed. A large-diameter particle sheet having a thickness of 0.5 to 0.7 μm is formed by applying a ceramic slurry containing a small-diameter ceramic powder on the upper layer, thereby forming an insulator green sheet. Was molded. The thickness of the small particle layer on the surface on which the internal conductor pattern is applied (the surface on which the internal conductor is formed) is 0.4 to 0.6 μm, and the average particle size of the small particles constituting the layer is 0.05 to 0.08 μm. did.

In the case of a three-layer structure in which small-diameter particle sheets are formed on both sides of a large-diameter particle sheet, a small-diameter particle sheet having a thickness of 0.5 to 0.7 μm is formed on a carrier film in advance. The above-mentioned molding was performed to produce an insulator green sheet having a three-layer structure.

In the insulator green sheet having the three-layer structure, the thickness of the small particle layer on the side on which the internal conductor pattern is applied (the side on which the internal conductor is formed) is 0.4 to 0.6 μm. The average particle diameter of the particles is 0.05 to 0.08 μm, the thickness of the small particle layer on the opposite surface (the side on which the internal conductor is not formed) is 0.5 μm, and the average particle diameter of the small particles constituting the particle layer is 0.5 μm. 08 to 0.12 μm.

This insulator green sheet is formed.
BaTiO3 is used for the large particle sheet and the small particle sheet.
Three0.2 mol part of MnO, YTwoOThreeTo
To the raw material composition containing 1 mol part and 1.0 mol part of MgO
On the other hand, the molar ratio is 0.5 SiO Two-0.2BaO-0.1
CaO-0.2LiTwoAdd 2 parts by weight of O
The produced ceramic powder is used.
An insulator ceramic slurry was prepared using the powder.

At this time, a small-diameter ceramic powder having an average particle diameter of 0.05 to 0.13 μm is used for the small-diameter particle sheet in the insulator green sheet, and an average particle diameter of 0.4 to 0.1 μm is used for the large-diameter particle sheet. A 6 μm large diameter ceramic powder was used.

The conductive paste has a particle size of 0.2 μm
An organic binder was mixed with 55% by weight of a vehicle with respect to 45% by weight of i powder and kneaded with a three-roll mill.

Next, the above-mentioned conductive paste was printed in the form of an internal conductor pattern on the main surface of the obtained insulator green sheet using a screen printing apparatus, and dried.

Next, this insulator green sheet was
Layers were laminated, and 10 layers of insulating green sheets each serving as an insulating layer were laminated on the upper and lower layers to form a temporary laminated molded body.

The provisional laminate formed under these conditions was in a state where the insulator green sheet was not completely adhered, and had a gap left for sufficient degassing at the next second lamination press. .

Next, the temporary laminated molded body was heated at a temperature of 100 ° C.
A second laminating press is performed at a pressure of 20 MPa, and the insulator green sheet coated with the inner conductor pattern and the insulator green sheets made of the same material as the upper and lower insulator green sheets are laminated and completely adhered to form a laminate. I got a body.

Next, the laminated molded body was cut into a lattice to obtain a molded body of the laminated body. One end of the internal conductor pattern of the internal conductor was alternately exposed at both end surfaces of the laminated molded body.

Next, the molded body of the laminate body was placed in the atmosphere 3
Heating was performed at 00 ° C. for 4 hours to perform a debubbling treatment.

Further, the molded body of the laminate body after de-buying is subjected to 1260 ° C. in an oxygen / nitrogen atmosphere of 10 −6 Pa.
For 2 hours, and further re-oxidized at 1000 ° C. in an oxygen-nitrogen atmosphere of 10 −2 Pa to obtain a ceramic sintered body. After firing, a Cu paste was baked on the end face of the ceramic sintered body at 900 ° C., and further, Ni / Sn plating was performed to form external electrodes connected to the internal conductor.

The external dimensions of the multilayer ceramic capacitor thus obtained are 1.1 mm wide and 2.0 mm long.
Met. The effective electrode area of one layer is 1.05 mm 2
Met. This multilayer ceramic capacitor was not deformed due to the insulator layer, and the inner conductor was flat without being curved.

As a comparative example, a multilayer ceramic capacitor was manufactured using an insulator green sheet formed only with a single particle size.

At this time, the thickness of the insulator layer in the insulator layer of the multilayer ceramic capacitor, the number of the small particle layers, the thickness of the large particle layer and the small particle layer, and the ceramic forming the large particle layer and the small particle layer Table 1 shows the average particle size of the large and small particles.

Next, the capacitance and dielectric breakdown voltage of each of the 100 multilayer ceramic capacitors were measured, and the short-circuit rate was evaluated. Measurements were taken at reference temperature 2
The measurement was performed at 5 ° C., and the following evaluation was performed on the multilayer ceramic capacitor obtained as described above.

First, the measurement was performed under the conditions of a frequency of 1.0 kHz and an input signal level of 0.5 Vrms.

From the capacitance, the electrode area and the dielectric thickness of each multilayer ceramic capacitor, and the number of layers,
The relative permittivity of the dielectric was calculated. Further, the short-circuit rate was calculated from the number of multilayer ceramic capacitors that were short-circuited during the measurement.

Further, the dielectric breakdown voltage was set to KIKUSUIDS
It was measured using M8103.

Next, the average particle size of the ceramic large particles and the small particles constituting the insulator layer was determined by an intercept method from an SEM photograph taken by using an electron microscope after breaking the obtained multilayer ceramic capacitor. .

The surface roughness (Ra) of the surface of the insulator layer was measured on the surface on which the internal conductor pattern was formed by using an atomic force microscope.

[0086]

[Table 1]

As is clear from the results in Table 1, Sample No. 1 was prepared by forming a small particle layer on one or both sides of a large particle layer. In 2 to 7 and 9 to 13, the thickness of the insulator layer is 3 μm
Even when the thickness was further reduced to 2.5 μm or less, the surface roughness (Ra) of the insulator layer was 90 nm or less in each case, and the occurrence of short circuit was 0%. Further, the dielectric constant was 3200 or more, and the dielectric breakdown voltage was 110 V or more.

In particular, Sample No. 1 in which a small particle layer was formed on both surfaces of a large particle layer. In each of 4 to 7, 10, 11, and 13, the dielectric breakdown voltage was higher than the samples in which the small particle layer was formed on one surface.

On the other hand, the sample N in which the small particle layer was not formed
o. In Examples 1 and 8, the surface roughness (Ra) of the insulator layer was 210 nm or more in both cases, the short-circuit rate was high, and the dielectric breakdown voltage was low and was 60 V or less.

[0090]

As described above in detail, the surface of the insulator layer is formed by forming the inner conductor side of the insulator layer with ceramic particles smaller in diameter than the ceramic particles constituting the central portion in the thickness direction of the insulator layer. The roughness (Ra) can be reduced, the variation in thickness can be reduced, and the dielectric breakdown voltage of the insulator layer can be increased.

Since the surface of the insulator green sheet becomes denser, the metal powder constituting the internal conductor pattern is prevented from entering the inside of the insulator green sheet, so that a short circuit defect can be eliminated.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a multilayer ceramic capacitor of the present invention.

FIG. 2 is an enlarged schematic sectional view showing the vicinity of an insulator layer and an internal conductor constituting the multilayer ceramic capacitor of FIG. 1;

FIG. 3 shows a process chart for manufacturing the ceramic laminate of the present invention.

[Explanation of symbols]

 9 Insulator layer 11 Internal conductor

Claims (6)

    [Claims]
  1. A plurality of insulator layers laminated on each other, an inner conductor interposed between the insulator layers, and an average particle size of the ceramic particles on the inner conductor side in the insulator layer is determined in a thickness direction. A ceramic laminate characterized by being smaller than the average particle size of the ceramic particles at the center.
  2. 2. The method according to claim 1, wherein the average particle size of the ceramic particles on the inner conductor side in the insulator layer is 0.3 μm or less, and the average particle size of the ceramic particles at the center in the thickness direction is 0.3 μm or more. The ceramic laminate according to claim 1, wherein:
  3. 3. The ceramic laminate according to claim 1, wherein the composition of the ceramic particles on the inner conductor side and the ceramic particles at the center in the thickness direction in the insulator layer are the same.
  4. 4. The ceramic laminate according to claim 1, wherein the thickness of the insulator layer is 3 μm or less.
  5. 5. A step of applying a ceramic slurry containing a large-diameter ceramic powder on a carrier film and applying a ceramic slurry containing a small-diameter ceramic powder on the surface thereof to form an insulator green sheet; Forming an internal conductor pattern on a part of the surface of the body green sheet, removing the carrier film, and forming a laminated molded body by laminating a plurality of the insulator green sheets on which the internal conductor pattern is formed. And a step of firing the laminated molded body.
  6. 6. A ceramic slurry containing a small-diameter ceramic powder is applied on a carrier film, a ceramic slurry containing a large-diameter ceramic powder is applied on the surface thereof, and a ceramic slurry containing a small-diameter ceramic powder is applied on the surface. 6. A method for producing a ceramic laminate according to claim 5, wherein an insulating green sheet is produced by applying a coating material.
JP2001097432A 2001-03-29 2001-03-29 Ceramic laminate and method of manufacturing the same Pending JP2002299145A (en)

Priority Applications (1)

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
JP2006237237A (en) * 2005-02-24 2006-09-07 Kyocera Corp Stacked ceramic capacitor
JP2007123480A (en) * 2005-10-27 2007-05-17 Kyocera Corp Laminated ceramic capacitor and its manufacturing method
JP2007123389A (en) * 2005-10-26 2007-05-17 Kyocera Corp Laminated electronic component
JP2007258661A (en) * 2005-09-28 2007-10-04 Kyocera Corp Laminated ceramic capacitor and its manufacturing method
JP2009123897A (en) * 2007-11-14 2009-06-04 Tdk Corp Ceramic electronic part, its manufacturing method and its packaging method
CN103390496A (en) * 2012-05-08 2013-11-13 三星电机株式会社 Multilayered ceramic elements
US20140071586A1 (en) * 2012-09-10 2014-03-13 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic electronic component and method of manufacturing the same

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JPH0562855A (en) * 1991-08-30 1993-03-12 Taiyo Yuden Co Ltd Laminated porcelain capacitor
JP2001110664A (en) * 1999-10-12 2001-04-20 Tdk Corp Laminated ceramic electronic parts and manufacturing method thereof

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JPH0562855A (en) * 1991-08-30 1993-03-12 Taiyo Yuden Co Ltd Laminated porcelain capacitor
JP2001110664A (en) * 1999-10-12 2001-04-20 Tdk Corp Laminated ceramic electronic parts and manufacturing method thereof

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006237237A (en) * 2005-02-24 2006-09-07 Kyocera Corp Stacked ceramic capacitor
JP4549203B2 (en) * 2005-02-24 2010-09-22 京セラ株式会社 Multilayer ceramic capacitor
JP2007258661A (en) * 2005-09-28 2007-10-04 Kyocera Corp Laminated ceramic capacitor and its manufacturing method
JP2007123389A (en) * 2005-10-26 2007-05-17 Kyocera Corp Laminated electronic component
JP2007123480A (en) * 2005-10-27 2007-05-17 Kyocera Corp Laminated ceramic capacitor and its manufacturing method
JP2009123897A (en) * 2007-11-14 2009-06-04 Tdk Corp Ceramic electronic part, its manufacturing method and its packaging method
JP4670856B2 (en) * 2007-11-14 2011-04-13 Tdk株式会社 Packaging method for ceramic electronic components
CN103390496A (en) * 2012-05-08 2013-11-13 三星电机株式会社 Multilayered ceramic elements
US20130301185A1 (en) * 2012-05-08 2013-11-14 Samsung Electro-Mechanics Co., Ltd. Multilayered ceramic elements
US20140071586A1 (en) * 2012-09-10 2014-03-13 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic electronic component and method of manufacturing the same
JP2014053584A (en) * 2012-09-10 2014-03-20 Samsung Electro-Mechanics Co Ltd Multilayer ceramic electronic component and manufacturing method therefor

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