KR101786473B1 - Multilayer ceramic capacitor - Google Patents

Multilayer ceramic capacitor Download PDF

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KR101786473B1
KR101786473B1 KR1020150126075A KR20150126075A KR101786473B1 KR 101786473 B1 KR101786473 B1 KR 101786473B1 KR 1020150126075 A KR1020150126075 A KR 1020150126075A KR 20150126075 A KR20150126075 A KR 20150126075A KR 101786473 B1 KR101786473 B1 KR 101786473B1
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hydrogen
external electrode
end faces
plating layer
sample
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KR20160030372A (en
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야스히로 니시사카
요시토 사이토
마코토 오가와
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가부시키가이샤 무라타 세이사쿠쇼
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/228—Terminals
    • H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/005—Electrodes
    • H01G4/008—Selection of materials
    • H01G4/0085—Fried electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/005—Electrodes
    • H01G4/012—Form of non-self-supporting electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/228—Terminals
    • H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
    • H01G4/2325—Terminals electrically connecting two or more layers of a stacked or rolled capacitor characterised by the material of the terminals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics

Abstract

The multilayer ceramic capacitor 1 is an element which forms hydrogen and a covalent bond hydride between the plating layer 13c of the outermost layer constituting the external electrode 13 and the dielectric layer 10 constituting the ceramic body 11 However, the element which generates a hydride having a boiling point of less than 125 ° C is excluded) and hydrogen and at least one element forming a hydride of the boundary region. As a result, it is possible to reduce the influence of hydrogen generated in the plating process and to prevent deterioration of the insulation resistance.

Description

[0001] MULTILAYER CERAMIC CAPACITOR [0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer ceramic capacitor, and more particularly to a structure of an external electrode or an internal electrode of a multilayer ceramic capacitor.

The multilayer ceramic capacitor includes a ceramic body composed of a plurality of laminated dielectric layers, a plurality of internal electrodes respectively disposed between the dielectric layers, and a pair of external electrodes formed on the ceramic body so as to conduct the internal electrodes. The surface of the external electrode is plated with Ni for preventing solder leaching during mounting. In order to improve solderability during soldering, Sn plating is applied on the Ni plated film. This plating of Ni, Sn, or the like is usually performed by electrolytic plating.

Japanese Patent Application Laid-Open No. 1-80011 discloses a method in which hydrogen ions are generated by a chemical reaction in a plating process and the hydrogen ions are occluded in internal electrodes to gradually reduce the surrounding dielectric layer, Thereby causing problems such as deterioration of resistance and the like. In the case of using an internal electrode containing a noble metal (for example, Ag-Pd alloy) as a main component, a metal (for example, Ni) for inactivating the absorption of hydrogen is added to the internal electrode .

However, in recent years, in order to reduce the material cost, a base metal such as Ni is used rather than a noble metal such as Ag or Pd as the material of the internal electrode. Japanese Patent Application Laid-Open No. 1-80011 discloses that Ni is a "metal that deactivates the absorption of hydrogen ", but according to research by the inventors and the like, even when the internal electrode is Ni, Which leads to deterioration of the device.

An object of the present invention is to provide a multilayer ceramic capacitor capable of reducing the influence of hydrogen generated in a plating process and preventing deterioration of insulation resistance.

As described above, conventionally, hydrogen generated in the plating process is thought to affect the deterioration of the insulation resistance. The inventors of the present invention have studied the deterioration of the insulation resistance described above and found that most of the hydrogen generated in the plating process is temporarily stored in the external electrode or the internal electrode and spread when the temperature is added and the voltage is applied to the multilayer ceramic capacitor, And reached the dielectric layer. The inventors of the present invention have completed the present invention by repeatedly experimenting and examining based on these findings.

A multilayer ceramic capacitor based on the first aspect of the present invention includes a ceramic body, a plurality of internal electrodes, and a pair of external electrodes. The ceramic body includes a plurality of laminated dielectric layers, and has both end faces opposing to each other and a plurality of side faces connecting the both end faces. The plurality of internal electrodes contain a base metal as a main component, are disposed between the stacked dielectric layers, and are alternately drawn out to both end faces. The pair of external electrodes includes an external electrode body formed on the ceramic body so as to be electrically connected to the internal electrodes extended to the both end faces of the ceramic body and at least one plating layer formed outside the external electrode body. In the multilayer ceramic capacitor according to the first aspect of the present invention, an element which forms a covalent hydride with hydrogen between the plating layer of the outermost layer and the dielectric layer of the plating layer (however, The element forming the hydride is excluded) and at least one element forming hydrogen and the hydride of the boundary region.

The element forming the covalent bond hydride with hydrogen (except for the element which generates hydride having a boiling point of less than 125 ° C) is a boron group (excluding In, Tl), carbon Group, nitrogen, oxygen, and halogen. The element forming hydrogen and the hydride in the boundary region is an element that forms a hydrogen-covalent hydride and an element that forms a metal-like hydride with hydrogen And refers to an element belonging to the boron group (excluding Al and Ga), group 11, and group 12 of the long period periodic table.

The plating layer of the outermost layer and the dielectric layer include not only the internal electrode and the external electrode body but also the interface between the plating layer of the outermost layer and the external electrode body, the interface between the external electrode body and the internal electrode, And the conductor is formed at the interface between the dielectric layer and the dielectric layer.

The element may be present between the outermost layer of the plated layer and the dielectric layer in its elemental form, or may be bonded to another element between the outermost plated layer and the dielectric layer. The hydrogen includes any of hydrogen, hydrogen, hydrogen, isotopes of hydrogen, and the like. The hydrogen referred to herein is mainly hydrogen generated by electrolysis in the plating process, but also includes water generated by a plating solution or condensation, or hydrogen present as water vapor in the atmosphere.

Here, in the multilayer ceramic capacitor based on the first aspect of the present invention, when the element is contained in the external electrode body, hydrogen is held in the external electrode body to suppress diffusion of hydrogen from the external electrode body It becomes possible.

In the multilayer ceramic capacitor according to the first aspect of the present invention, when the element is contained in the internal electrode, hydrogen is held in the internal electrode to suppress diffusion of hydrogen from the internal electrode to the dielectric layer It becomes possible.

A multilayer ceramic capacitor based on the second aspect of the present invention includes a ceramic body, a plurality of internal electrodes, and a pair of external electrodes. The ceramic body includes a plurality of laminated dielectric layers, and has both end faces opposed to each other and a plurality of side faces connecting the end faces. The plurality of internal electrodes contain a base metal as a main component, are disposed between the stacked dielectric layers, and are alternately drawn out to both end faces. The pair of external electrodes includes an external electrode body formed on the ceramic body so as to be electrically connected to the internal electrodes extended to the both end faces of the ceramic body and at least one plating layer formed outside the external electrode body. The multilayer ceramic capacitor according to the second aspect of the present invention is characterized in that an interface between the internal electrode and the external electrode body, an external surface of the external electrode body, an interior of the external electrode body, an interface between the internal electrode and the dielectric layer, An element that forms a covalent bond hydride with hydrogen at the interface between the plating layer on the outermost layer and the plating layer on the inner side when the plating layer includes a plurality of layers And a hydrogen holding film containing at least one of hydrogen and an element forming a hydride in the boundary region.

In the above, the hydrogen retention film may be formed continuously, or may be partially present, or may exist in the form of a mesh, a line, or the like.

In the multilayer ceramic capacitor according to the first and second aspects of the present invention, the element may be at least one selected from the group consisting of Sn, Bi, Al, Ag, Zn, Au, In, Ga, It is desirable to be species.

The diffusion of hydrogen to the dielectric layer can be suppressed since Sn, Bi, Al, Ag, Zn, Au, In, Ga, Ge and Si are bonded to hydrogen after they are held.

On the other hand, among these elements, Sn, Bi and Al are particularly preferable elements because they have a low melting point and are easy to form an alloy.

The multilayer ceramic capacitor based on the first aspect of the present invention is an element which forms hydrogen and a covalent bond hydride between the plated layer of the outermost layer and the dielectric layer (except for an element which generates hydride having a boiling point of less than 125 캜) And at least one element forming hydrogen and a hydride in the boundary region. Therefore, hydrogen generated in the plating process can be maintained between the plating layer and the dielectric layer in the outermost layer. As a result, diffusion of hydrogen to the dielectric layer can be suppressed, and deterioration of the insulation resistance IR can be prevented.

In the multilayer ceramic capacitor according to the second aspect of the present invention, the interface between the inner electrode and the outer electrode body, the outer surface of the outer electrode body, the inner surface of the outer electrode body, the interface between the inner electrode and the dielectric layer, (Except for an element which generates a hydride having a boiling point of less than 125 deg. C) and hydrogen (hydrogen) at the interface between the outermost layer of the plated layer and the plating layer on the inner side thereof, And a hydrogen-retaining film containing at least one of the elements forming hydrides in the boundary region. Therefore, hydrogen can be held by the hydrogen retention film to suppress diffusion of hydrogen to the dielectric layer.

On the other hand, the hydrogen-retaining film may be formed by a combination of an interface between the internal electrode and the dielectric layer, an interface between the internal electrode and the external electrode body, an external surface of the external electrode body, an interface between the internal electrode and the dielectric layer, It may be disposed at one of the interface between the outermost layer of the plated layer and the inner plated layer. However, it is also possible to arrange them in two or more.

These and other objects, features, aspects and advantages of the present invention will become apparent from the following detailed description of the invention, which is to be understood in connection with the accompanying drawings.

1 is a cross-sectional view of a multilayer ceramic capacitor according to Embodiment 1 of the present invention.
2 is a view for explaining a junction between internal electrodes and external electrode bodies of a multilayer ceramic capacitor according to Embodiment 1 of the present invention.
3 is a mapping diagram of Sn obtained by analyzing a cross-section of a multilayer ceramic capacitor according to Embodiment 1 of the present invention by the FE-WDX method (electrolytic radiation-wavelength dispersive X-ray analysis method).
4 is a cross-sectional view of a multilayer ceramic capacitor according to Embodiment 2 of the present invention.
5 is a cross-sectional view of a multilayer ceramic capacitor according to Embodiment 3 of the present invention.
6 is a cross-sectional view of a multilayer ceramic capacitor according to Embodiment 4 of the present invention.
7 is a cross-sectional view of a multilayer ceramic capacitor according to Embodiment 5 of the present invention.

[Embodiment 1]

A multilayer ceramic capacitor 1 according to a first embodiment of the present invention will be described with reference to Fig. The multilayer ceramic capacitor 1 includes a ceramic body 11, a plurality of internal electrodes 12, and a pair of external electrodes 13. The ceramic body 11 includes a plurality of laminated dielectric layers 10 and has both end faces 11a facing each other and a plurality of side faces 11b connecting the end faces 11a. The plurality of internal electrodes 12 are respectively disposed between the stacked dielectric layers 10 and alternately drawn out to both end faces 11a of the ceramic body 11. [ The pair of external electrodes 13 are formed so as to be electrically connected to the internal electrodes 12.

The ceramic body 11 has a substantially rectangular parallelepiped shape including both end faces 11a and four side faces 11b and has a rounded portion with chamfered corners and corners. As the material constituting the dielectric layer 10, a BaTiO 3 -based dielectric ceramics is used. In addition as the material constituting the dielectric layers (10), CaTiO 3, SrTiO 3, can use the dielectric ceramics as a main component, such as CaZrO 3.

The internal electrodes 12 are alternately exposed on both end faces 11a of the ceramic body 11. [ As the conductive material constituting the internal electrode 12, a material containing Ni as a main component is used. In addition, as the conductive material constituting the internal electrode 12, a base metal mainly composed of Cu or the like can be used.

The outer electrode 13 is formed on both end faces 11a of the ceramic body 11 and includes an outer electrode body 13a formed to be electrically connected to the inner electrode 12, (13b, 13c). The external electrode body 13a is formed by applying a conductive paste containing metal powder and glass to the end face 11a of the ceramic body 11 and firing it. As the material constituting the external electrode main body 13a, a metal containing Cu as a main component is used. In addition, as the material constituting the external electrode main body 13a, a conductive material containing Ni or the like as a main component may be used. The thickness of the external electrode body 13a such as Ni is, for example, 1 to 100 占 퐉.

The plating layers 13b and 13c are composed of a plating layer 13b formed on the outer surface of the outer electrode body 13a and an outermost plating layer 13c formed on the outer surface of the plating layer 13b. Ni is used as the material of the plating layer 13b, and Sn is used as the material of the plating layer 13c. As the plating layer 13c of the outermost layer, metals such as Pd, Cu, and Au may be used. The thickness of each of the plating layers 13b and 13c is, for example, 0.1 to 20 占 퐉. The plating layers 13b and 13c are formed by electrolytic plating. On the other hand, the plating layer is not necessarily composed of a plurality of layers, but may be composed of one layer of metal such as Cu.

In the multilayer ceramic capacitor 1 of this embodiment, hydrogen and a covalent bond type hydride are formed in the conductive path body 15 connecting the plating layer 13b on the surface of the external electrode body 13a and the dielectric layer 10 (Except for an element that generates a hydride having a boiling point of less than 125 캜) and at least one element (a hydrogen-retaining element) that forms hydrogen and a hydride in the boundary region.

Particularly, in the multilayer ceramic capacitor of this embodiment, the external electrode main body 13b constituting a part of the above-described conductive path body 15 contains the hydrogen holding element.

Here, the conductive path member 15 is a conductive path formed between the plating layer 13b on the surface of the external electrode body 13a and the dielectric layer 10, and the internal electrode 12 and the external electrode main body 13a, Are included. It is also preferable that an interface between the plating layer 13b and the external electrode main body 13a or an interface between the external electrode main body 13a and the internal electrode 12 or an interface between the internal electrode 12 and the dielectric layer 10 If it is formed, it is also included.

The element forming the covalent bond hydride with hydrogen (except for the element which generates hydride having a boiling point of less than 125 캜) is a boron group of the long period periodic table (such as B, Al, Ga ), Carbon (C, Si, Ge, Sn, Pb), nitrogen (N, P, As, Sb, Bi), oxygen (O, S, Se, Te, Po) I, At). The element forming hydrogen and the hydride in the boundary region is an element at the boundary between an element forming hydrogen and a covalent bond hydride and an element forming hydrogen and a metal bond hydride, Refers to an element belonging to the boron group (In, Tl except Al and Ga), Group 11 (Cu, Ag, Au), Group 12 (Zn, Cd, Hg). These elements form stable compounds with hydrogen. That is, once bound to hydrogen, energy is required to release the hydrogen, which makes it difficult to release hydrogen. By using this property, hydrogen generated in the plating process can be held in the conductive path body 15 described above.

In order to contain the hydrogen holding element in the external electrode main body 13a constituting a part of the conductive path element 15, in this embodiment, in the conductive paste for forming the external electrode main body 13a, A powder of a hydrogen-retaining element (a hydrogen-retaining metal powder) is blended. The proportion of the hydrogen-retaining metal powder to be incorporated in the conductive paste is preferably 1 to 40 vol% in terms of the solid content ratio.

On the other hand, the hydrogen-retaining metal may be present in the outer electrode main body 13a as a single metal, or may be dispersed or alloyed with other metals in the outer electrode main body 13a, as the case may be.

Here, the cross section of the multilayer ceramic capacitor 1 in which Sn was added as the hydrogen holding element was observed by the FE-WDX method (electrolytic radiation-wavelength dispersive X-ray analysis).

Fig. 3 is a graph showing the results of analysis of the cross-section of the multilayer ceramic capacitor 1 in which the external electrode main body 13a is formed by using a conductive paste containing Cu as a main component with Sn as a hydrogen-retaining metal by the FE-WDX method. Hydrogen-retaining metal).

The sample for analysis is obtained by polishing the multilayer ceramic capacitor 1 along the direction perpendicular to the end face 11a of the ceramic body 11 and the dielectric layer 10 of the uppermost layer until the volume becomes about 1/2 , And a polishing sag of the internal electrode was milled. Then, the sample prepared as described above was analyzed by the FE-WDX method under the following conditions.

Acceleration voltage: 15.0 kV

Irradiation current: 5 × 10 -8 A

Magnification: 3000 times

DwellTime (acquisition time in one pixel): 40 ms

Analysis depth: 1 ~ 2㎛

As a result, as shown in FIG. 3, Sn is present in the external electrode body 13a and part of the lead portion 12a of the internal electrode 12 drawn out to the end face 11a of the ceramic body 11 exists .

≪ Evaluation test >

In order to confirm the significance of the multilayer ceramic capacitor 1 of the present embodiment, it was confirmed that a metal powder (Sn, Bi, Ag, Pd) of another kind as shown in Table 1 was added to a conductive paste containing Cu powder as a conductive component Samples Nos. 1 to 5 of Table 1 were prepared using conductive paste without conductive paste and metal powder.

On the other hand, detailed specifications of the conductive paste were as follows.

Solid content: 25 vol%

The ratio of the Cu powder in the solid component: 70 vol%

The ratio of the glass in the solid content: 25 vol%

The ratio of the additive metal powder in the solid content: 5 vol%

Particle size of Cu powder: 3 탆

Glass particle size: 2 탆

Composition of glass: BaO-SrO-B 2 O 3 -SiO 2 glass frit (glass frit containing 10 to 50 wt% of BaO, 3 to 30 wt% of B 2 O 3 , SiO 2 : 3 to 30 wt% glass is used)

In preparing samples of samples Nos. 1 to 5, the conductive paste was applied to the end face 11a of the ceramic body 11 and fired to form the external electrode body 13a.

Thereafter, a plating layer 13b made of Ni was formed on the outside of the external electrode body 13a by electrolytic plating, and a plating layer 13c made of Sn was formed on the outside by electrolytic plating.

As a result, Samples 1 to 5 of Table 1 were obtained.

The multilayer ceramic capacitor thus manufactured is usually a capacitor having a capacity of 10 kV, a rated voltage of 6.3 V, a length of 1.0 mm, a width of 0.5 mm and a height of 0.5 mm, and the thickness of the external electrode body 13a is 25 m The thickness of the plating layer 13b is 3 m, and the thickness of the plating layer 13c is 3 m.

The samples of Sample Nos. 1 to 5 of Table 1 thus produced were subjected to a PCBT test.

The PCBT test was conducted under the conditions of a temperature of 125 ° C, a relative humidity of 95%, an applied voltage of 3.2 V, and a load time of 72 hours. The insulation resistance (IR) was measured for each sample. When the IR value at the end of the test was 0.5 lower than the IR value at the start of the test, the IR deterioration was regarded as Log IR. On the other hand, the number of each sample is 20.

The results are shown in Table 1.

Figure 112015086562344-pat00001

In Table 1, the samples of Sample Nos. 1 to 3 satisfy the requirements of the present invention, and the samples of Sample Nos. 4 and 5 do not satisfy the requirements of the present invention.

As shown in Table 1, the sample of Sample No. 1 containing Sn in the external electrode body 13a and the sample of Sample No. 2 containing Bi contained no IR deterioration. In addition, the sample of Sample No. 3 in which Ag was contained in the external electrode main body 13a was less likely to generate IR deterioration.

On the other hand, in the sample of the sample No. 4 containing Pd in the external electrode main body 13a, especially in the sample of the sample No. 5 in which no metal was added, IR deterioration was found to be many.

As described above, since the multilayer ceramic capacitor 1 of this embodiment contains the hydrogen-retaining element in the external electrode main body 13a, hydrogen generated in the plating process forms part of the conductive path body 15 And can be absorbed and held by the external electrode body 13a. As a result, the diffusion of hydrogen to the dielectric layer 10 can be suppressed, and deterioration of the insulation resistance IR can be prevented.

On the other hand, in the present invention, good results can be obtained even when the hydrogen-retaining element such as Sn is present inside the internal electrode 12. In addition, good results can be obtained even when Bi and Al are present instead of Sn.

In the present invention, it is preferable that at least one of Sn, Bi, and Al as the hydrogen holding element is largely segregated at the junction portion of the internal electrode 12 and the external electrode main body 13a.

Here, the above-described junction between the internal electrode 12 and the external electrode body 13a will be described with reference to Fig. The junction between the internal electrode 12 and the external electrode main body 13a is defined by the end face 12a of the internal electrode 12 exposed on the end face 11a of the ceramic body 11 and the end face 12a of the ceramic body 11 Refers to an intermediate point R0 between one end (upper end in Fig. 2) R1 and the other end (lower end in Fig. 2) R2 in the region R in contact with the outer electrode main body 13a formed in the outer electrode body 13a.

That is, at least one of Sn, Bi, and Al is largely segregated at the junction between the internal electrode 12 and the external electrode main body 13a. At least one of Sn, Bi, (Joining portion) indicating that a large amount of segregation occurs.

In this embodiment, the external electrode main body 13a has a single-layer structure. However, the external electrode main body 13a may have a multilayer structure, and one or more layers of the external electrode main body 13a may have hydrogen- It is also possible to constitute such that it contains.

[Embodiment 2]

A multilayer ceramic capacitor 1A according to a second embodiment of the present invention will be described with reference to FIG. In this multilayer ceramic capacitor 1A, as shown in Fig. 4, a hydrogen-holding film 13e is formed at the interface between the external electrode body 13a and the internal electrode 12 as shown in Fig. On the other hand, in the configuration common to the multilayer ceramic capacitor 1 of the first embodiment, the same reference numerals are assigned to the multilayer ceramic capacitor 1A of the second embodiment, and description thereof is not repeated. The same applies to the other Embodiments 3 to 5 below.

In the multilayer ceramic capacitor 1A, an element which forms a covalent bond hydride with hydrogen at the interface between the external electrode main body 13a and the internal electrode 12 (except for an element which generates a hydride having a boiling point of less than 125 占 폚 And a hydrogen holding film 13e containing at least one of hydrogen and an element forming a hydride in the boundary region. The hydrogen holding film 13e is continuously formed on the end face 11a of the ceramic body 11 so as to cover the lead portion 12a of the internal electrode exposed on the end face 11a. However, the hydrogen retention film 13e may not be continuous, partially exist, or may exist in the form of a mesh, a line, or the like.

The hydrogen holding film 13e is formed by spattering a hydrogen holding element (hydrogen holding metal) in a metal state and is formed in a state of a metal film on the end face 11a of the ceramic body 11. [ On the other hand, the hydrogen retention film 13e can be formed by vapor deposition, plating or the like.

≪ Evaluation test >

In order to confirm the significance of the multilayer ceramic capacitor 1A of this embodiment, a sample including a film formed by sputtering another kind of metal (Sn, Bi, Al, Ag, Zn, Pd, Ti) Samples 6 to 12 were prepared. In addition, specimen No. 13 in which the hydrogen retention film was not formed without sputtering was produced. The film thickness of the hydrogen retention film 13e was set at 1 mu m.

On the other hand, the thickness of the external electrode main body 13a was set to 15 mu m (the central portion of the cross section). The conductive paste for forming the external electrode main body 13a had a solid content of 25 vol% and a glass content in the solid content of 25 vol%.

Samples Nos. 6 to 13 of Table 2 thus prepared were tested under the same conditions as those of the PCBT test conducted in the above-described Embodiment 1.

The results are shown in Table 2.

Figure 112015086562344-pat00002

In Table 2, the samples of Sample Nos. 6 to 10 satisfy the requirements of the present invention, and the samples of Sample Nos. 11 to 13 do not satisfy the requirements of the present invention.

As shown in Table 2, IR deterioration was not observed in the specimen No. 6 having the Sn film as the hydrogen retention film 13e, the specimen No. 7 having the Bi film, and the specimen No. 8 having the Al film. Further, the sample of the sample No. 9 provided with the Ag film and the sample of the sample No. 10 provided with the Zn film were less likely to generate IR deterioration.

As a result, a sample of the sample No. 11 in which the Pd film was formed by the spatter, and a sample of the sample No. 12 in which the Ti film was formed was found to have a high IR deterioration. In particular, in the sample of the sample No. 13 in which the spatter was not applied, IR deterioration was recognized in many cases.

Even when the hydrogen holding film 13e is provided at the interface between the external electrode main body 13a and the internal electrode 12 from the above-described results, the hydrogen generated in the plating process is absorbed by the hydrogen holding film 13e It is possible to suppress or prevent hydrogen from diffusing into the dielectric layer 10 through the internal electrode 12. [

Although the hydrogen-holding film 13e is continuously formed on the end face 11a of the ceramic body 11 so as to cover all of the lead-out portions 12a of the internal electrodes in the second embodiment, It is possible to obtain a significant effect even when it exists partially in the section 11a, or in the form of a mesh, a line, or the like.

[Embodiment 3]

5 is a view showing a multilayer ceramic capacitor 1B according to Embodiment 3 of the present invention. In this multilayer ceramic capacitor 1B, the hydrogen holding film 13f is formed inside the external electrode body 13a. Specifically, the external electrode main body 13a is composed of two layers of an external electrode main body 13a 1 containing Ni as a main component and an external electrode main body 13a 2 containing Cu as a main component, The hydrogen retention film 13f which is an almost continuous film having conductivity is formed.

The hydrogen retention film 13f is formed by mixing a hydrogen-retaining metal with a conductive paste for forming the second outer electrode body 13a 2, applying the conductive paste to the first outer electrode body 13a 1, And external electrode main bodies 13a 1 and 13a 2 of two layers.

The ratio of the hydrogen-retaining metal added to the conductive paste is preferably in the range of 1 to 40 vol%.

≪ Evaluation test >

In order to confirm the significance of the multilayer ceramic capacitor 1B of this embodiment, other kinds of metal powders (Sn, Bi, Ag, Zn, Pd) shown in Table 3 were added to the conductive paste containing Cu powder as a conductive component Samples 14 to 19 of Table 3 were prepared using one conductive paste and a conductive paste to which no metal powder was added.

On the other hand, the addition amount of the metal powder to the conductive paste for forming the second external electrode main body 13a 2 was set at a ratio of the solid content ratio of 5vol% in the conductive paste. The other specifications were the same as those of the first embodiment.

On the other hand, the specification of the conductive paste for forming the first external electrode main body 13a 1 was as follows.

Solid content: 15 vol%

The proportion of the components in the solid content: 40 vol%

The ratio of the glass in the solid content: 25 vol%

Particle size of Ni powder: 0.5 탆

Particle size of the blank: 100 nm to 500 nm

The samples of Sample Nos. 14 to 19 of Table 3 thus prepared were tested under the same conditions as the PCBT test in the above-mentioned Embodiment 1. [

The results are shown in Table 3.

Figure 112015086562344-pat00003

In Table 3, the samples of Sample Nos. 14 to 17 satisfy the requirements of the present invention, and the samples of Sample Nos. 18 and 19 do not satisfy the requirements of the present invention.

As shown in Table 3, no IR deterioration was found in the sample of Sample No. 14 in which Sn was blended in the external electrode main body 13a 2 of the second layer and the sample of Sample No. 15 in which Bi was blended. In addition, the sample of Sample No. 16 in which Ag was blended and the sample of Sample No. 17 in which Zn was blended showed less IR deterioration.

On the other hand, in the sample of the sample No. 18 in which Pd was blended in the external electrode main body 13a 2 of the second layer, much IR deterioration occurred. In particular, in the sample No. 19 in which the metal powder was not added, IR deterioration was more likely to occur.

5, since the hydrogen generated in the plating process is absorbed by the hydrogen holding film 13f, hydrogen is prevented from passing through the internal electrode 12, It is confirmed that the diffusion of light into the light emitting layer 10 is suppressed and prevented, and the deterioration of IR is suppressed.

On the other hand, in the case of Embodiment 3, it is preferable that the hydrogen holding film 13f is a continuous film, but it is not necessarily formed as a continuous film, but is partially present along the surface of the external electrode body 13a 1 Or may exist in the form of a mesh, a line, or the like. Further, it is not necessary that the film is a uniform thickness, and it may be formed so that the distribution of the hydrogen-retaining metal differs in the thickness direction.

[Embodiment 4]

6 is a view showing a multilayer ceramic capacitor 1C according to Embodiment 4 of the present invention. In this multilayer ceramic capacitor 1C, a hydrogen-retaining film 13g containing a hydrogen-retaining element is formed on the outer surface of the outer electrode main body 13a between the surface of the outer electrode main body 13a and the plated layer 13b, Respectively.

The hydrogen holding film 13g is formed by spattering a hydrogen holding element (hydrogen holding metal) in a metal state, and is formed in a state of a metal film on the surface of the external electrode body 13a. Further, the hydrogen holding film 13g is continuously formed so as to cover the entire surface of the external electrode body 13a. On the other hand, the hydrogen retention film 13g may be formed by vapor deposition, plating or the like.

≪ Evaluation test >

A sample including a film formed by sputtering another kind of metal (Sn, Bi, Al, Ag, Pd, Ti) to confirm the significance of the multilayer ceramic capacitor 1C of this embodiment, 25 samples were produced. In addition, specimen No. 26 in which the hydrogen retention film was not formed without spattering was produced. On the other hand, the specifications of the conductive paste for forming the external electrode main body 13a were the same as those in the second embodiment.

The samples of Sample Nos. 20 to 26 of Table 4 thus prepared were tested under the same conditions as those of the PCBT test in Embodiment 1 described above.

The results are shown in Table 4.

Figure 112015086562344-pat00004

In Table 4, the samples of Sample Nos. 20 to 23 satisfy the requirements of the present invention, and the samples of Sample Nos. 24 to 26 do not satisfy the requirements of the present invention.

As shown in Table 4, IR deterioration was not observed in the specimen No. 20 in which the Sn film was provided as the hydrogen retention film 13g, in the specimen No. 21 in which the Bi film was provided, and in the specimen No. 22 in which the Al film was provided. In addition, the sample of the sample No. 23 provided with the Ag film had less IR deterioration.

On the other hand, in the sample of the sample No. 24 in which the Pd film was formed by the sputtering and in the sample of the sample No. 25 in which the Ti film was formed, much IR deterioration was recognized. In addition, in the sample of the sample No. 26 in which the spatter was not applied, the IR deterioration was recognized in many cases.

In the multilayer ceramic capacitor 1C, on the other hand, the hydrogen retention film 13g is partially present between the surface of the external electrode body 13a and the plating layer 13b, or may be in the form of a mesh, Or may exist. In this case, a significant effect can be obtained.

[Embodiment 5]

7 is a view showing a multilayer ceramic capacitor 1D according to Embodiment 5 of the present invention. In this multilayer ceramic capacitor 1D, a hydrogen-retaining film 13h containing a hydrogen-retaining element is formed between the plating layer 13c on the outermost layer and the plating layer 13b on the inside thereof.

The hydrogen holding film 13h is formed by spattering a hydrogen holding element (hydrogen holding metal) in a metal state, and is formed in the state of a metal film on the outer surface of the plating layer 13b. Further, the hydrogen holding film 13h is continuously formed so as to cover the entire surface of the plating layer 13b. On the other hand, the hydrogen retention film 13h can be formed by vapor deposition, plating or the like.

≪ Evaluation test >

In order to confirm the significance of the multilayer ceramic capacitor 1D of this embodiment, a sample including a film formed by sputtering another kind of metal (Sn, Bi, Ag, Pd) A sample was prepared. In addition, specimen No. 31 in which the hydrogen retention film was not formed without sputtering was produced. On the other hand, the specifications of the conductive paste for forming the external electrode main body 13a were the same as those in the second embodiment.

Samples Nos. 27 to 31 of Table 5 thus prepared were tested under the same conditions as those of the PCBT test conducted in the above-described Embodiment 1.

The results are shown in Table 5.

Figure 112015086562344-pat00005

In Table 5, the samples of Sample Nos. 27 to 29 satisfy the requirements of the present invention, and the samples of Sample Nos. 30 to 31 do not satisfy the requirements of the present invention.

As shown in Table 5, the sample of the sample No. 27 provided with the Sn film, the sample of the sample No. 28 provided with the Bi film, and the sample of the sample No. 29 provided with the Ag film were fewer in IR deterioration as the hydrogen holding film 13h.

On the other hand, in the sample of the sample No. 30 in which the Pd film was formed by the sputtering, IR deterioration was observed to be considerable. In addition, in the sample of the sample No. 31 in which the sputtering was not performed, IR deterioration was observed in many cases.

On the other hand, also in the case of the multilayer ceramic capacitor 1D, the hydrogen retention film 13h may be partially present between the plating layer 13b and the plating layer 13c, or may exist in the form of a mesh, a line, or the like . In this case, a significant effect can be obtained.

The characteristic constitution of the multilayer ceramic capacitor according to Embodiments 1 to 5 described above can be combined with each other as required.

While the embodiments of the invention have been described, it should be understood that the embodiments disclosed herein are illustrative in all respects and not restrictive. It is intended that the scope of the invention be indicated by the appended claims, and that all changes which come within the meaning and range of equivalency of the claims are intended to be embraced therein.

Claims (5)

A ceramic body including a plurality of laminated dielectric layers and having opposite end faces and a plurality of side faces connecting the end faces,
A plurality of internal electrodes which are disposed between the stacked dielectric layers and which are alternately drawn out to the both end faces and which contain a base metal as a main component,
An outer electrode body formed on the ceramic body so as to conduct (communicate with) the inner electrode drawn out to both end faces of the ceramic body; and a pair of outer electrodes having a plated layer formed on the outer side of the outer electrode body Which is a multilayer ceramic capacitor,
Wherein at least one of Sn, Bi, Al, and Zn is contained in the external electrode body. A ceramic body including a plurality of stacked dielectric layers and having opposite end faces opposing each other and a plurality of side faces connecting the end faces,
A plurality of internal electrodes which are disposed between the stacked dielectric layers and which are alternately drawn out to both end faces,
An outer electrode body formed on the ceramic body so as to be electrically connected to the inner electrodes drawn to both end faces of the ceramic body; and a pair of outer electrodes having a plurality of plating layers formed on the outer side of the outer electrode body, Lt;
Wherein at least one of Sn, Bi, Al and Zn is contained in at least one of the external electrode main body and the plating layer formed between the plating layer of the outermost layer and the plating layer of the plurality of plating layers and between the external electrode main body Multilayer Ceramic Capacitors. delete A ceramic body including a plurality of stacked dielectric layers and having opposite end faces opposing each other and a plurality of side faces connecting the end faces,
A plurality of internal electrodes which are disposed between the stacked dielectric layers and which are alternately drawn out to both end faces,
An external electrode body formed on the ceramic body so as to be electrically connected to the internal electrodes extended to both end faces of the ceramic body; and a pair of external electrodes having at least one layer of plating layer formed outside the external electrode body A ceramic capacitor,
A plating layer of an outermost layer in the case where the plating layer includes a plurality of layers, and a plating layer in the inside of the outer electrode body in the case where the plating layer includes a plurality of layers, And at least one of B, Al, Ga, C, Si, Ge, Sn, Pb, N, P, As, Sb, Bi, O, S, Se, Te, Po, Further comprising a hydrogen holding film containing at least one element selected from the group consisting of I, At, In, Tl, Au, Zn, Cd and Hg. 5. The method of claim 4,
Wherein the element is at least one selected from the group consisting of Sn, Bi, Al, Zn, Au, In, Ga, Ge and Si.
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