JP2003017356A - Laminated electronic component and manufacturing method therefor - Google Patents

Laminated electronic component and manufacturing method therefor

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Publication number
JP2003017356A
JP2003017356A JP2001197119A JP2001197119A JP2003017356A JP 2003017356 A JP2003017356 A JP 2003017356A JP 2001197119 A JP2001197119 A JP 2001197119A JP 2001197119 A JP2001197119 A JP 2001197119A JP 2003017356 A JP2003017356 A JP 2003017356A
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Prior art keywords
dielectric
internal electrode
layer
non
electronic component
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JP2001197119A
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JP3527899B2 (en
Inventor
Tomohiro Iwaida
智広 岩井田
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Kyocera Corp
京セラ株式会社
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Priority to JP2001197119A priority Critical patent/JP3527899B2/en
Priority claimed from GB0419635A external-priority patent/GB2402103B/en
Priority claimed from US10/155,702 external-priority patent/US7089659B2/en
Publication of JP2003017356A publication Critical patent/JP2003017356A/en
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Publication of JP3527899B2 publication Critical patent/JP3527899B2/en
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Abstract

(57) [Problem] Even when the number of stacked dielectric ceramic layers is increased by reducing the thickness thereof, a step due to the thickness of the internal electrode layer can be eliminated and cracks and delamination can be suppressed. Provided is a multilayer electronic component and a method for producing the same. An internal electrode layer (9) and an internal electrode layer extension (11) form substantially the same plane without any level difference, and a dielectric ceramic layer (7b) of a non-capacitive part (3) is replaced with a dielectric ceramic layer (7a) of a capacitive part (1).
It was made of porcelain having higher sinterability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated electronic component and a method of manufacturing the same, and more particularly, to a laminated electronic component such as a wiring board or a laminated ceramic capacitor in which dielectric ceramic layers and internal electrode layers are thinly laminated. And its manufacturing method.

[0002]

2. Description of the Related Art In recent years, with the miniaturization and high-density mounting of electronic equipment, multilayer electronic components mounted in the electronic equipment are required to be thin and have high dimensional accuracy. Capacitors are required to be small and have high capacitance,
For this reason, the dielectric ceramic layers and the internal electrode layers are being made thinner and multilayered.

In such a laminated electronic component, the thickness of the internal electrode layers formed between the dielectric ceramic layers has a great influence as the dielectric ceramic layers are made thinner and multilayered. The step due to the thickness of the internal electrode layer is accumulated between the portion where the is formed and the portion where the is not formed,
Adhesion between surrounding dielectric ceramic layers without internal electrode layers becomes weak, and delamination and cracks easily occur. For this reason, efforts have been made to eliminate the step on the dielectric ceramic layer.

As such a laminated electronic component, for example, one disclosed in Japanese Patent Laid-Open No. 2000-311831 is known. In the multilayer ceramic capacitor disclosed in this publication, a dielectric powder containing a dielectric powder having the same composition as the dielectric powder in the dielectric green sheet is provided around the internal electrode pattern formed on the main surface of the dielectric green sheet. A body pattern is formed adjacent to the internal electrode pattern.

According to such a manufacturing method, since the step due to the thickness of the internal electrode layer can be substantially eliminated, the dielectric ceramic layers can be laminated without being affected by the thickness of the internal electrode layer. it can.

[0006]

However, in the multilayer electronic component disclosed in the above-mentioned Japanese Patent Laid-Open No. 2000-311831, the dielectric pattern formed to eliminate the step due to the internal electrode layer is a dielectric pattern. Since it is formed of a material having the same composition as the body green sheet, the firing shrinkage in the thickness direction of the dielectric pattern is smaller than the firing shrinkage in the thickness direction of the internal electrode layers. There is a problem in that the bonding strength at the interface with and becomes weak and delamination occurs around the internal electrode layers.

Further, since the bonding strength at the interface between the dielectric porcelain layer and the internal electrode layer is weak, cracks are generated around the internal electrode layer of the laminated electronic component or at the edges during soldering or thermal shock test. There was a problem.

Delamination and cracks due to the difference in firing shrinkage between the dielectric porcelain layer and the internal electrode layer are more likely to occur as the dielectric porcelain layer is made thinner.
If the thickness is less than μm, there is a problem that it tends to occur.

Therefore, according to the present invention, even when the number of laminated layers is increased by thinning the dielectric porcelain layer, the step due to the thickness of the internal electrode layers can be eliminated and the occurrence of cracks and delamination can be suppressed. An object is to provide a laminated electronic component and a method for manufacturing the same.

[0010]

In the laminated electronic component of the present invention, the internal electrode layer is formed so as to extend on the side surface of a capacitor portion formed by alternately laminating dielectric ceramic layers and internal electrode layers. A non-capacitance portion including the extended internal electrode layer extension portion and the dielectric porcelain layer is integrally formed, and the non-capacitance portion is provided with a pair of external electrodes alternately connected to the internal electrode layer extension portion. In the multilayer electronic component, the internal electrode layer and the internal electrode layer extended portion form substantially the same plane without a step, and the dielectric ceramic layer of the non-capacitance portion is a dielectric of the capacitance portion. It is characterized in that it is made of porcelain having a sinterability higher than that of the porcelain layer.

According to this structure, the step due to the internal electrode layer extending portion in the non-capacitance portion can be eliminated, and the non-capacitance portion has a higher sinterability than the capacitance portion. , The density and mechanical strength of the non-capacitance part are increased,
It is possible to prevent delamination and cracks around the internal electrode layers.

In the above laminated electronic component, the dielectric ceramic layers of the capacitance part and the non-capacity part are composed of dielectric particles and a glass phase, and the amount of glass contained in the dielectric ceramic layer of the non-capacity part is It is desirable that the amount is larger than the amount of glass contained in the dielectric ceramic layer of the capacitance portion.

As described above, since glass is present between the dielectric particles of the dielectric porcelain layer forming the capacitance portion and the non-capacity portion, the capacitance portion and the non-capacitance portion can be formed without affecting the dielectric characteristics. The sinterability of the dielectric porcelain layer can be controlled, and in particular, the sinterability of the non-capacitance portion can be improved by increasing the glass amount of the non-capacity portion as compared with the capacitance portion.

In the above-mentioned laminated electronic component, the average particle diameter of the dielectric particles forming the dielectric ceramic layer of the non-capacitance portion is smaller than the average particle diameter of the dielectric particles forming the dielectric ceramic layer of the capacitance portion. That is desirable.

By thus reducing the average particle diameter of the dielectric particles of the dielectric ceramic layer forming the non-capacitance portion as compared with the average particle diameter of the dielectric particles of the dielectric ceramic layer forming the capacitance portion. The sinterability and mechanical strength of the non-capacity part can be further enhanced, and cracks can be prevented.

In the method of manufacturing a laminated electronic component of the present invention, a step of printing a plurality of internal electrode patterns at predetermined intervals by printing an internal electrode paste on the main surface of a dielectric green sheet containing a dielectric powder. And a dielectric paste containing at least a dielectric powder and a glass powder and having a sinterability higher than that of the dielectric green sheet is printed between the internal electrode patterns, and is substantially the same as the internal electrode patterns. The method is characterized by including a step of forming a dielectric pattern having a thickness and a step of laminating a plurality of dielectric green sheets on which the internal electrode patterns and the dielectric patterns are formed.

According to this structure, by forming the dielectric pattern between the internal electrode patterns, it is possible to easily eliminate the step due to the internal electrode patterns, and further to stack a plurality of dielectric green sheets. Also, it is possible to prevent the above-mentioned dielectric green sheet from falling between the internal electrode patterns, and thus it is possible to prevent deformation of the multilayer electronic component.

Further, since the dielectric pattern has high sinterability, it is possible to easily increase the bonding strength between the dielectric ceramic layer and the internal electrode layer in the non-capacitance portion, and prevent delamination and cracks.

In the method for manufacturing the above-mentioned laminated electronic component, since the softening point of the glass powder contained in the dielectric pattern is lower than the softening point of the glass powder contained in the dielectric green sheet, the non-capacitance portion can be easily fired. It can increase the shrinkage rate and promote densification.

In the method for manufacturing the above-mentioned laminated electronic component, the average particle size of the dielectric powder contained in the dielectric paste is made smaller than the average particle size of the dielectric powder contained in the dielectric green sheet, thereby facilitating the process. The firing shrinkage rate of the non-capacitance part can be increased and densification can be promoted. It can be raised and cracks can be prevented.

[0021]

(Structure) The multilayer electronic component of the present invention is applied to, for example, a multilayer ceramic capacitor as shown in FIG.

In the monolithic ceramic capacitor of the present invention, the non-capacitance portion 3 which does not exhibit the dielectric characteristic is integrally formed on both side surfaces of the capacitance portion 1 which exerts the dielectric characteristic, and the non-capacitance portion 3 is exposed. A pair of external electrodes 5 is provided at each end.

The capacitor portion 1 is constructed by alternately laminating dielectric ceramic layers 7a and internal electrode layers 9.

On the other hand, the non-capacitance portion 3 is composed of an internal electrode layer extension portion 11 formed by extending the internal electrode layer 9 formed inside the capacitance portion 1 and a dielectric ceramic layer 7b, The internal electrode layer 9 formed in the capacitance portion 1 and the internal electrode layer extension portion 11 formed in the non-capacity portion 3 are formed on the same plane without any step.

In other words, each of the internal electrode layers 9 is connected to the external electrode 5 via the internal electrode layer extending portion 11 and the external electrode 5 of the internal electrode 9 not connected to the external electrode 5 is included.
On the side, the dielectric porcelain layer 7 having almost the same thickness as the internal electrode layer 9 is provided.
b is formed.

The thickness of the dielectric porcelain layer 7a which constitutes the capacitor portion 1 is set to 3 μm or less for the reason that the multilayer electronic component is made thin and multi-layered in order to make the capacity high and the capacitance is high. The thickness of the dielectric ceramic layer 7a is preferably 1.5 to 3 μm for the reason of its dielectric property.

On the other hand, as described above, the thickness of the dielectric ceramic layer 7b forming the non-capacitance portion 3 enhances the bonding at the interface between the internal electrode layer 9 forming the capacitance portion 1 and the dielectric ceramic layer 7a. At the same time, it is preferable that the internal electrode layer extension portion 11 is formed thinner than the capacitance portion 1 side so as not to prevent the state where the internal electrode layer extension portion 11 is flush with the internal electrode layer 9.

The width W of the non-capacitance portion 3 is preferably 100 μm or less for the reason that the effective area of the internal electrode layer 9 forming the capacitance portion 1 is increased and the electrostatic capacitance is increased. From the reason of increasing the width, the width of the non-capacitance portion 3 is preferably in the range of 50 to 100 μm.

As shown in FIG. 2, the dielectric porcelain layer 7a forming the capacitance portion 1 is composed of a mixed phase of dielectric particles 13 such as barium titanate and a glass phase 15. In particular, when a base metal is used for the internal electrode layer 9, it is necessary to use a material that is resistant to reduction, because firing is necessary in a reducing atmosphere.

On the other hand, the dielectric porcelain layer 7b forming the non-capacitance portion 3 is also composed of a mixed phase of the dielectric particles 13 such as barium titanate and the glass phase 15 like the capacitance portion 1, and the capacitance portion 1 and the non-capacitance portion 3 are preferably made of substantially the same phase so that the firing shrinkage start temperatures thereof are brought close to each other and the dielectric characteristics of the capacitance portion 1 are not affected.

Here, it is important that the sinterability of the dielectric ceramic layer 7b of the non-capacitance portion 3 is higher than the sinterability of the capacitance portion 1. Therefore, the glass amount of the non-capacity portion 3 is equal to that of the capacitance portion 1. It is desirable that the amount is larger than the glass amount.

Further, the dielectric porcelain layer 7 constituting the capacitance section 1
It is desirable that the average particle diameter of the dielectric particles 13 of a is 0.2 μm or more. In a high multilayer ceramic capacitor having 200 or more stacked layers, the dielectric porcelain layer of the capacitance section 1 composed of the dielectric particles 13 is used. 7a has a thin layer of 0.3 to 0.
8 μm is desirable.

On the other hand, the average particle diameter of the dielectric particles 13 forming the dielectric ceramic layer 7b of the non-capacitance portion 3 requires high strength, and therefore the dielectric particles forming the dielectric ceramic layer 7a of the capacitance portion 1 is required. It is composed of dielectric particles 13 having an average particle size smaller than 13, and is preferably 0.45 μm or less.
It is desirable that the thickness is 0.1 to 0.45 μm.

The glass phase 15 contained in the dielectric porcelain layer 7a forming the capacitance section 1 contains an alkali metal oxide and is composed of an amorphous phase mainly composed of SiO 2 , CaO, BaO and the like. Is composed of these glass phases 15
Exist between the dielectric particles 13 and part of the dielectric particles 13
A compound such as a BaSiO-based compound is formed between and.

On the other hand, the dielectric porcelain layer 7b forming the non-capacitance portion 3 also contains the same glass phase 15 as that of the capacitance portion 1. Due to this glass phase 15, the density of the non-capacitance portion 3 is increased. Therefore, the mechanical strength can be improved.

Further, the dielectric porcelain layer 7 constituting the capacitance section 1
The amount of the glass phase 15 contained in a is preferably 0.2 to 5% by weight, and in particular 0.9 to 2.6 for the reason that the contraction rates of the dielectric porcelain layer 7a and the internal electrode layer 9 are matched. Weight percent is preferred.

On the other hand, the amount of glass contained in the dielectric porcelain layer 7b forming the non-capacitance portion 3 is larger than the amount of glass contained in the dielectric porcelain layer 7a forming the capacitance portion 1 of the dielectric porcelain layer 7b. It is desirable for the reason of increasing the sinterability, and its glass amount is 0.8 to 25% by weight, particularly 2.7 to 1%.
4.1 wt% is more desirable.

Then, the glass phase content G of the capacity part 1
c 1 and the glass phase content of the non-capacity part 3 is Gc 2 ,
The weight ratio of Gc 1 / Gc 2 is preferably in the range of 0.03 to 0.9.

On the other hand, the internal electrode layer 9 is made of a metal film obtained by sintering a film of a conductive paste, and a base metal such as Ni, Co, Cu is used as the conductive paste. In addition, the internal electrode layer 9 is a conductor film having a substantially rectangular shape with the base metal as the main phase in this way, and the inside of the odd layers of the first layer, the third layer, the fifth layer, ... The electrode layer 9 is connected to the internal electrode layer extending portion 11, one end of the internal electrode layer extending portion 11 is exposed at one end surface of the non-capacitance portion 3, and the second layer and the fourth layer are arranged from the top. The sixth and sixth internal electrode layers 9 are connected to the internal electrode layer extending portion 11 on the other side, and one end of the internal electrode layer extending portion 11 is exposed at the other end surface of the non-capacitance portion 3. is doing. The external electrode 5 and the internal electrode layer 9 do not necessarily have to be made of the same material.

On the other hand, the thickness of the internal electrode layer 9 is preferably 2 μm or less, and in order to reduce the amount of metal contained in the internal electrode layer 9 and to secure a sufficient effective area, it is particularly preferable that the internal electrode layer 9 has a thickness of 0.5 to 0.5 μm. It is preferably 1.5 μm.

The thickness ratio between the dielectric porcelain layer 7a and the internal electrode layer 9 that form the capacitance part 1 is t 1 when the thickness of the dielectric porcelain layer 7a that forms the capacitance part 1 is equal to the thickness of the internal electrode layer 9. when the t 2 and when t 2 / t 1> 0.2, a and t 2 <2 [mu] m, dielectric ceramic layer 7b constituting the non-capacity portion 3 of the present invention is preferably applied, more In order to suppress delamination and the like due to the excessive thickness of the internal electrode layer 9, the thickness ratio t 2 / t 1 is preferably 0.2 to 0.75.

The end surface of the internal electrode layer 9 formed on the dielectric ceramic layer 7a is formed so as to be an inclined surface having an acute angle with respect to the dielectric ceramic layer 7a, and the peripheral edge of the internal electrode layer 9 is formed. The dielectric ceramic layer 7b of the non-capacitance portion 3 may be formed so as to overlap the portion.

The number of laminated layers of the laminated electronic component of the present invention is determined by the dielectric ceramic layers 7a constituting the laminated electronic component,
7b has a thin multilayer structure, and a step due to the thickness of the internal electrode layer 9 is accumulated between the portion where the internal electrode layer 9 is formed and the portion where the internal electrode layer 9 is not formed on the dielectric ceramic layers 7a and 7b. However, the surrounding dielectric ceramic layer 7 without the internal electrode layer 9
From the reason that the adhesion between a and 7b can be increased and delamination and cracks can be suppressed, it is desirable that the number of layers is 100 or more in order to reduce the size and capacity of the multilayer electronic component.

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

As shown in FIG. 3A, the dielectric ceramic layer 7
Dielectric green sheet 2 having a thickness of 1.5 to 4 μm and serving as a
1 is manufactured using the slip casting method. Specific examples of the slip casting method include a pulling 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.

The thickness of the dielectric green sheet 21 is preferably 2.5 to 4 μm for reasons of small size, large capacity and high insulation.

As the dielectric material, specifically, BaT
Ceramic powders such as iO 3 -MnO-MgO-Y 2 O 3 are used because they have resistance to reduction, and glass powder is added to this dielectric powder as a sintering aid.

The average particle size of the dielectric powder used for the dielectric green sheet 21 is preferably 1.5 μm or less for the reason that the dielectric green sheet 21 is made thin, and also has high dielectric properties and high dielectric properties. 0.1 for that reason
0.9 μm is desirable.

As the glass powder to be added to the dielectric green sheet 21 together with the dielectric powder, the SiO--CaO--BaO system glass containing an alkali metal oxide suppresses the influence on the dielectric properties and increases the shrinkage rate by firing. It is preferably used because it increases the density.

Further, the amount of glass powder contained in the dielectric green sheet 21 enhances the sinterability of the dielectric green sheet 21 and enhances the dielectric characteristics.
The content is preferably 0.5 to 5% by weight with respect to the dielectric powder, and more preferably 1 to 3% by weight for the reason that the density, mechanical strength and dielectric properties of the dielectric ceramic layer 7a are enhanced.

The average particle size of the glass powder used for the dielectric green sheet 21 is determined by the dielectric green sheet 21.
1.5 μm or less is desirable for the reason of high sintering and high densification, and it is 0.
1 to 0.9 μm is desirable.

BaTi which is the main raw material of the dielectric powder
There are solid-phase method, liquid-phase method (method of passing oxalate, etc.), and hydrothermal synthesis method for synthesizing O 3 powder. Among them, the hydrothermal synthesis method has a narrow particle size distribution and high crystallinity. Is desirable. The average specific surface area of the BaTiO 3 powder is 1.1.
It is preferably 10 m 2 / g.

Next, as shown in FIG. 3B, a conductive paste is used on the surface of the dielectric green sheet 21 by a known printing method such as screen printing, gravure printing, offset printing or the like. The internal electrode pattern 23 is formed. The thickness is preferably 2 μm or less, particularly 1.5 μm or less from the viewpoint of miniaturization and high reliability of the capacitor.

This conductive paste contains metal particles, an organic solvent containing a mixture of an aliphatic hydrocarbon and a higher alcohol, an organic binder containing ethyl cellulose soluble in the organic solvent, and an organic solvent containing the organic solvent. An organic binder made of a sparingly soluble epoxy resin is contained.

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,
Ni is desirable because the firing temperature of the metal is the same as the firing temperature of general dielectrics and the cost is low.

The average particle size of the base metal particles is set to 0. to improve the dispersibility of the metal powder and prevent the metal from becoming large during firing.
The range of 1 to 0.5 μm is desirable. The average particle size of the base metal is preferably 0.15 to 0.4 μm because a dense and smooth metal film is formed.

In addition to the metal powder, a fine dielectric powder is preferably mixed with the conductive paste in order to suppress the sinterability of the internal electrode pattern 23, and the conductive paste is used. In order to form a uniform particle size and improve the smoothness, the particle size of the dielectric powder is 0.05 to
0.3 μm is desirable.

The epoxy resin contained in the conductive paste is preferably 0.05 to 1.5% by weight with respect to the ethyl cellulose contained together.

Next, as shown in FIG. 3C, a dielectric paste is applied between the internal electrode patterns 23 formed on the surface of the dielectric green sheet 21 to form a dielectric pattern 25. This dielectric paste can be formed by a known method such as a screen printing method, a gravure printing method, an offset printing method, an ink jet method, a relief printing method. The dielectric pattern 25 has a thickness corresponding to the thickness of the internal electrode pattern 23.

Further, in the dielectric paste for forming the dielectric pattern 25, for example, the dielectric green sheet 21 and the dielectric pattern 25 are integrated and the amount of glass powder is increased in order to enhance the sinterability. It is desirable to include it.

The average particle size of the dielectric powder contained in this dielectric paste may be the same as the average particle size of the dielectric powder used for the dielectric green sheet 21, but preferably, the dielectric green is used. It is smaller than the dielectric powder used for the sheet 21 and preferably 1 μm or less.
The average particle size is particularly preferably 0.05 to 0.7 μm because the firing shrinkage rate can be easily controlled in relation to the internal electrode layer 9 and the mechanical strength can be increased without abnormal grain growth.

The glass powder to be added to the dielectric pattern 25 together with the dielectric powder has the same SiO-CaO-BaO system as the dielectric green sheet 21 due to the fact that firing shrinkage is matched and high density is achieved. Glass powder to which a substance is added is preferably used. The softening point of this glass powder can be changed by the amount of alkali metal oxide.

The amount of the glass powder used in the dielectric paste is 1 with respect to the dielectric powder for the reason that the sinterability of the dielectric ceramic layer 7b of the non-capacitance portion 3 is increased and the mechanical strength is increased. Addition of -25 wt% is desirable in order to suppress cracking and delamination, and in particular, 3-15 wt% is desirable from the viewpoint of enhancing the thermal shock resistance.

The average particle size of the glass powder used for the dielectric paste is preferably 1.5 μm or less as compared with the glass powder used for the dielectric green sheet 21 because of high sintering and high density. Further, 0.07 to 0.7 μm is desirable because of the high strength of the non-capacitance portion 3.

Further, the softening point of the glass powder used for this dielectric paste is preferably lower than the softening point of the glass powder used for the dielectric green sheet 21, and the dielectric ceramic layer 7b of the non-capacitance part 3 is the capacitance part. It shrinks more than the dielectric ceramic layer 7a of No. 1 and has high density and high strength, and delamination and cracks can be suppressed.

The dielectric paste is an organic material composed of a dielectric powder containing an alkali metal oxide used in the dielectric green sheet 21, SiO-CaO-BaO glass powder, and a mixture of an aliphatic hydrocarbon and a higher alcohol. It contains a solvent, an organic binder composed of ethyl cellulose soluble in the organic solvent, and an organic binder composed of an epoxy resin which is hardly soluble in the organic solvent.

Further, the dielectric paste is applied to the peripheral portion of the internal electrode pattern 23 and the dielectric green sheet 21 is formed on the upper surface, or is transferred to the periphery of the internal electrode pattern 23 on the dielectric green sheet 21. Is also good.

Next, as shown in FIG. 3 (d), a plurality of dielectric green sheets 21 coated with a conductive paste are laminated and the temperature is 25 to 80 ° C. and the pressure is 0.1 to 10 MPa.
Then, the first lamination is carried out to form a temporary laminated molded body.
At this time, the laminated dielectric green sheets 21 are not completely adhered to each other, and a gap is left to allow sufficient degassing during the next second lamination. This is because the epoxy resin has a high glass transition point Tg (120 ° C.) and therefore does not plasticize when heated and pressed at 25 to 80 ° C.

Next, this temporary laminated compact is heated to a temperature of 90 to 13.
The second laminating press is performed at 0 ° C. and a pressure of 10 to 100 MPa to completely adhere the two to obtain a laminated compact.

In the laminated molded body of the present invention, the dielectric pattern 25 is formed together with the internal electrode pattern 23 on one main surface of the dielectric green sheet 21 on which the internal electrode pattern 23 is formed. Dielectric green sheet 21 and internal electrode pattern 23 by heating and pressing
It is possible to form a laminated molded body without causing the deformation.

Next, this laminated compact is cut into a lattice shape to obtain an electronic component main body compact. On both end surfaces of this molded body, one ends of the internal electrode patterns 23 serving as the internal electrode layers 9 and the internal electrode layer extending portions 11 are alternately exposed.

The molded body of the electronic component main body is not limited to the above-mentioned method, and any molded body in which the thinned dielectric green sheets 21 and the internal electrode patterns 23 are alternately laminated can be manufactured. A method such as slurry dipping may be used.

Next, the molded body of the electronic component main body is de-heated in the air at 250 to 300 ° C. or at 500 to 800 ° C. in a low oxygen atmosphere having an oxygen partial pressure of 0.1 to 1 Pa, and then 1200 in a non-oxidizing atmosphere. Bake at ˜1300 ° C. for 2-3 hours.
Further, if desired, the reduced electronic component body is oxidized by performing reoxidation treatment at 900 to 1100 ° C. for 5 to 15 hours under a low oxygen partial pressure of oxygen partial pressure of about 0.1 to 10 −4 Pa, An electronic component body having high capacitance and dielectric characteristics can be obtained.

Finally, a Cu paste is applied to each end face of the obtained electronic component body, Ni / Sn plating is applied, and the external electrode 5 electrically connected to the internal electrode layer extending portion 11 is formed. Then, a monolithic ceramic capacitor is manufactured.

(Operation) As described above, the dielectric ceramic layer 7a
And an internal electrode layer 9 are alternately laminated on the side surface of the capacitor portion 1, the internal electrode layer extending portion 11 formed by extending the internal electrode layer 9 and a dielectric ceramic layer 7b. Non-capacity part 3
Are integrally formed, and the internal electrode layer 9 of the capacitance section 1 and the non-capacity section 3 are formed.
The internal electrode layer extending portion 11 of the non-capacitance portion 3 forms the same plane with substantially no step, and the dielectric ceramic layer 7 of the non-capacitance portion 3
Since b is made of a porcelain having a sinterability higher than that of the dielectric porcelain layer 7a of the capacitance section 1, it is possible to eliminate a step due to the internal electrode layer extending section 11 in the non-capacity section 3, and Since the non-capacitance portion 3 has a higher sinterability than the capacitance portion 1, the dielectric ceramic layer 7b and the internal electrode layer extension portion 1
The mechanical strength in the vicinity of the interface with 1 becomes high, and delamination and cracks around the internal electrode layers can be prevented.

[0076]

Example A monolithic ceramic capacitor, which is one of the ceramic laminates, was manufactured as follows.

The dielectric green sheet is made of BaTiO 3 9
0.5 mol% of Y 2 O 3 and MgO with respect to 100 mol% of a composition consisting of 9.5 mol% and 0.5 mol% of MnO
Of 0.5% by mole, and a dielectric ceramic slurry having a composition containing the glass powder in the softening point and the addition amount shown in Table 1 was applied to a belt-shaped carrier film made of polyester by a die coater method to have a thickness of 3 μm. The dielectric green sheet of was formed into a film. The average particle size of the dielectric powder is dominated by the BaTiO 3 powder having a large content.
The average particle diameter of O 3 was used.

Here, the average particle diameter of the dielectric powder used for the dielectric green sheet is about 0.4 μm, the average particle diameter of the glass powder is about 0.7 μm, and the softening point is 680 ° C. Dielectric green sheets were produced by adding the amounts shown in Table 1.

The conductive paste has an average particle size of about 0.2 μm.
Of 45% by weight of Ni powder to 5.5% of ethyl cellulose
% By weight and 55% by weight of a vehicle consisting of 94.5% by weight of petroleum alcohol were kneaded with a three-roll mill.

A dielectric paste for a dielectric pattern is obtained by crushing a part of the above dielectric ceramic slurry until the average particle size of BaTiO 3 reaches the average particle size shown in Table 1 and forming a paste in the same manner as the conductive paste. Prepared.

As the glass powder, the glass powder containing the above-mentioned components and having the softening point shown in Table 1 was used, and the amount shown in Table 1 was added to 100 parts by weight of the dielectric powder. The average particle size of the glass powder was about 0.5 μm.

Next, as shown in FIG. 3B, the conductive paste described above is printed in an internal electrode pattern on the main surface of the obtained dielectric green sheet using a screen printing device. Dried.

Further, as shown in FIG. 3C, the dielectric paste is printed and dried by screen printing around the internal electrode pattern formed on the dielectric green sheet, and the dielectric pattern is formed together with the internal electrode pattern. A dielectric green sheet formed by coating was produced.

Next, as shown in FIG. 3 (d), 200 layers of dielectric green sheets are laminated, and the dielectric green sheets on which the internal electrode patterns and the dielectric patterns to be the dielectric layers are not formed are formed on the upper and lower layers thereof. Ten sheets were laminated to form a temporary laminated molded body.

In the temporary laminated body produced under these conditions, the dielectric green sheets were not completely adhered to each other, and a gap was left to allow sufficient degassing at the next second laminating press. .

Next, this temporary laminated compact was heated at a temperature of 100.degree.
The second lamination press is performed at a pressure of 20 MPa, and the dielectric green sheets coated with the internal electrode patterns and the dielectric green sheets made of the same material as the upper and lower dielectric green sheets are laminated and completely adhered to form a laminate. Got the body

Since the laminated molded body to be the laminated electronic component of the present invention has the dielectric pattern formed with the internal electrode pattern on one main surface of the dielectric green sheet having the internal electrode pattern formed thereon, In the pressing step, the laminated green body could be formed without deformation of the dielectric green sheet or the internal electrode pattern due to heating and pressing.

Next, this laminated molded body was cut into a lattice shape to obtain a molded body of the electronic component body. One end of the internal electrode pattern forming the internal electrode layer extending portion was alternately exposed on both end faces of this laminated compact.

Next, the molded body of the electronic component body was subjected to 500 in an oxygen / nitrogen atmosphere at 250 ° C. or 0.1 Pa in the atmosphere.
By heating to ℃, de-bye treatment was performed.

Further, with respect to the molded body of the electronic component body after removal of the by-pass, in an oxygen / nitrogen atmosphere of 10 −7 Pa, 1250
After firing for 2 hours at 0 ° C, reoxidation treatment was performed at 900 ° C for 4 hours in an oxygen-nitrogen atmosphere of 10 -2 Pa to obtain an electronic component body. After firing, Cu is applied to the end surface of the ceramic sintered body.
The paste was baked at 900 ° C. and further plated with Ni / Sn to form an external electrode connected to the internal electrode layer.

The outer dimensions of the monolithic ceramic capacitor thus obtained are 0.8 mm in width and 1.6 mm in length.
Met. Further, there was no step due to the internal electrode layer, and this internal electrode layer was flat without being curved.

With respect to the obtained monolithic ceramic capacitors, 1000 samples were observed with a 40-fold binocular microscope to evaluate the presence or absence of cracks on the end faces of the monolithic ceramic capacitors.

Further, each of 300 samples was polished from the end face and the side face of the sintered body, and the presence or absence of delamination at the peripheral portion of the internal electrode layer was evaluated.

Using the monolithic ceramic capacitors obtained as described above, the capacitance was measured for each of 300 samples under the conditions of a frequency of 1.0 kHz and a measurement voltage of 0.5 Vrms, and the average value was obtained. Was calculated. next,
For each 300 samples, a thermal shock resistance test at a temperature (ΔT = 280 ° C.) was performed based on JIS standard, and the number of cracks was evaluated.

Further, each of the 10 laminated ceramic capacitors was subjected to cross-section polishing and then heat-etched to obtain an electron microscope (SE
M) Observation was performed, and the SEM photograph was image-analyzed to determine the porosity in the dielectric porcelain layer forming the capacitive part and the non-capacitive part. Further, the glass amount was measured for Si using an analytical electron microscope (EPMA), and was determined based on the composition of the standard sample.

The average particle size of the dielectric particles forming the capacitance part of the multilayer ceramic capacitor manufactured here was 0.42 μm in all the samples.

[0097] The average particle size of the dielectric powder (BaTiO 3 powder) and glass powder used in the dielectric powder (BaTiO 3 powder) and glass powder, and the dielectric paste used in the dielectric green sheets, on the stage The powder dispersed in 100 was measured with an electron microscope for 100 particles, and the average value was calculated. The above results are summarized in Table 1.

[0098]

[Table 1]

From the results shown in Table 1, the sample No. in which the amount of glass in the dielectric ceramic layer constituting the non-capacitance portion was made larger than the amount of glass in the dielectric ceramic layer constituting the capacitance portion. In 1 to 10,
Sample No. In 9 and 10, although a slight decrease in capacitance was observed due to the amount of glass in the dielectric ceramic layer,
The porosity of the non-capacity part after firing was lower than that of the capacity part, and the sinterability was high. Almost no cracks or delaminations were observed, and particularly in the thermal shock test, no increase in cracks was observed.

Further, the softening point of the glass powder in the dielectric paste was made lower than that of the glass powder in the dielectric green sheet, with the same amount of glass in the dielectric ceramic layers forming the non-capacitance portion and the capacitance portion. Sample No. Also in Nos. 11 and 12, the porosity of the non-capacity part after firing was lower than that of the capacity part, and the crack, delamination, and thermal shock test could be improved.

Further, the average particle size of the dielectric powder in the dielectric paste is calculated from the average particle size in the dielectric green sheet with the same amount of glass in the dielectric ceramic layers forming the non-capacitance part and the capacitance part. Sample No. Also in Nos. 13 and 14, the porosity was reduced, and cracks and delamination after firing could be improved.

Then, the average particle size of the dielectric powder in the dielectric paste is made smaller than the average particle size in the dielectric green sheet, and the amount of glass in the dielectric ceramic layer forming the non-capacitance part is set to the capacitance part. Sample No. 1 having a larger amount than the glass in the dielectric ceramic layer constituting the In Nos. 15 to 16, the capacitance of the monolithic ceramic capacitor was increased, and cracks, delamination, and thermal shock test (ΔT crack) after firing could be eliminated.

On the other hand, Sample No. 3 having the same amount of glass in the dielectric ceramic layers constituting the non-capacitance portion and the capacitance portion, the softening point of the glass powder and the average particle diameter of the dielectric particles were the same. In No. 17, since the non-capacitance portion and the capacitance portion had close firing shrinkage rates and had the same porosity, the internal electrode layer extension portions and the dielectric portions were not formed due to the high firing shrinkage percentage of the internal electrode layer extension portions. The bonding strength at the interface with the body porcelain layer was weakened, cracks and delamination were increased, and particularly, the mechanical strength was weak, so the number of cracks increased in the thermal shock test.

Sample No. 1 in which the amount of glass added to the dielectric paste to be the non-capacity part was smaller than the amount of glass added to the dielectric green sheet to be the capacity part. 18 and sample No. 18 in which the average particle size of the dielectric powder used for the dielectric paste is increased. In No. 19, the porosity of the non-capacity part after firing was smaller than that of the capacity part, and cracks and delamination were further increased.

[0105]

As described above in detail, the internal electrode layers and the internal electrode layer extension portions form substantially the same plane without steps, and the dielectric porcelain layer forming the non-capacitance portion is connected to the capacitance portion. By using a porcelain having a sinterability higher than that of the dielectric porcelain layer to configure, it is possible to eliminate the step due to the internal electrode layer extended portion in the non-capacitance portion, and, in comparison with the capacitance portion, Since the non-capacitance portion has high sinterability, the mechanical strength in the vicinity of the interface between the dielectric ceramic layer and the internal electrode layer is increased, and delamination and cracks around the internal electrode layer can be prevented.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a multilayer electronic component of the present invention.

FIG. 2 is an enlarged schematic view of a capacitive part and a non-capacitive part that compose the multilayer electronic component of the present invention.

FIG. 3 is a process drawing for manufacturing the multilayer electronic component of the present invention.

[Explanation of symbols]

1 ... Capacity section 3 ... Non-capacity part 5 ... External electrodes 7a, 7b ... Dielectric porcelain layer 9 ... Internal electrode layer 11 ... Internal electrode layer extension 13 ... Dielectric particles 15: Glass phase 21 ... Dielectric green sheet 23: Internal electrode pattern 25 ... Dielectric pattern

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F100 AA34 AD00 AG00A AG00C                       AG00E AL05 AR00B AR00D                       AR00E BA02 BA03 BA04                       BA05 BA08 BA10A BA10C                       BA10D BA10E DE01A DE01C                       DE01E EJ42 EJ422 EJ48                       EJ48A EJ48C EJ48E EJ482                       EJ86 EJ862 JG05A JG05C                       JG05E JG06A JG06C JG06E                       JG10B JG10D JG10E JK20                       JL11                 5E001 AB03 AH01 AH09 AJ01 AJ02                 5E082 AA01 AB03 FG06 FG26 FG46

Claims (6)

[Claims]
1. An internal electrode layer extended portion formed by extending the internal electrode layer on a side surface of a capacitance portion formed by alternately laminating dielectric ceramic layers and internal electrode layers, and a dielectric ceramic layer. A non-capacitance portion integrally formed of and a pair of external electrodes that are alternately connected to the internal electrode layer extending portion in the non-capacitance portion is a laminated electronic component, the internal electrode layer and The internal electrode layer extending portion forms substantially the same plane without a step, and the dielectric porcelain layer of the non-capacitance portion is made of porcelain having a sinterability higher than that of the dielectric porcelain layer of the capacitance portion. A laminated electronic component characterized by the above.
2. The dielectric porcelain layer of the capacity part and the dielectric porcelain layer of the non-capacity part are composed of dielectric particles and a glass phase, and the amount of glass contained in the dielectric porcelain layer of the non-capacity part is The multilayer electronic component according to claim 1, wherein the laminated electronic component is larger than the amount of glass contained in the dielectric porcelain layer of the capacitor portion.
3. The average particle diameter of the dielectric particles forming the non-capacitance dielectric ceramic layer is smaller than the average particle diameter of the dielectric particles forming the capacitance dielectric ceramic layer. The multilayer electronic component according to claim 1.
4. A step of printing an internal electrode paste on a main surface of a dielectric green sheet containing a dielectric powder to form a plurality of internal electrode patterns at predetermined intervals, and between the internal electrode patterns. A step of printing a dielectric paste containing at least a dielectric powder and a glass powder and made of a material having a higher sinterability than the dielectric green sheet to form a dielectric pattern having substantially the same thickness as the internal electrode pattern. And a step of laminating a plurality of dielectric green sheets on which the internal electrode patterns and the dielectric patterns are formed, the method for producing a laminated electronic component.
5. The method for producing a multilayer electronic component according to claim 4, wherein the softening point of the glass powder contained in the dielectric pattern is lower than the softening point of the glass powder contained in the dielectric green sheet. .
6. The laminate according to claim 4, wherein the average particle size of the dielectric powder contained in the dielectric paste is smaller than the average particle size of the dielectric powder contained in the dielectric green sheet. Molded electronic parts manufacturing method.
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US10/155,702 US7089659B2 (en) 2001-05-25 2002-05-24 Method of producing ceramic laminates
GB0212030A GB2376207B (en) 2001-05-25 2002-05-24 Method of producing ceramic laminates,laminated electronic parts and method of producing the same
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