JPH05129152A - Laminated porcelain capacitor and its manufacture - Google Patents

Laminated porcelain capacitor and its manufacture

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Publication number
JPH05129152A
JPH05129152A JP31408991A JP31408991A JPH05129152A JP H05129152 A JPH05129152 A JP H05129152A JP 31408991 A JP31408991 A JP 31408991A JP 31408991 A JP31408991 A JP 31408991A JP H05129152 A JPH05129152 A JP H05129152A
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JP
Japan
Prior art keywords
porcelain
electrode layer
laminated
internal electrode
unfired
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP31408991A
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Japanese (ja)
Other versions
JP2945529B2 (en
Inventor
Hiroshi Kishi
Hiroshi Saito
弘志 岸
博 齋藤
Original Assignee
Taiyo Yuden Co Ltd
太陽誘電株式会社
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Abstract

PURPOSE:To prevent the occurrence of cracks at the time of having brought high-temperature solder into contact with a laminated porcelain capacitor. CONSTITUTION:An outside electrode layer is made by applying conductive paste wherein grain growth suppressing matter is mixed, on a laminated green chip, and the growth suppressing matter is diffused into porcelain by baking this so as to produce small particle diameter area 21a in the vicinities of outside electrode layers 24 and 25.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly reliable laminated ceramic capacitor and a method for manufacturing the same.

[0002]

2. Description of the Related Art As shown in FIG. 3, first and second internal electrode layers 2 are formed in a dielectric ceramic layer 1 of barium titanate or the like.
A multilayer ceramic capacitor having a structure in which 3 is provided and the first and second external electrode layers 4 and 5 connected to these are provided is widely used.

[0003]

By the way, when the laminated ceramic capacitor is attached to the circuit board, the first and second external electrode layers 4 and 5 are connected to the wiring conductor by soldering.
When high-temperature solder comes into contact with the first and second external electrode layers 4 and 5 in this soldering process, thermal shock is applied to the porcelain layer 1,
Cracks 6 near the boundary between the external electrode layers 4 and 5 and the porcelain layer 1
May occur. Although this kind of crack does not directly affect the capacitance, it may lead to a decrease in mechanical strength and a decrease in reliability.

Therefore, a first object of the present invention is to provide a highly reliable laminated ceramic capacitor. A second object of the present invention is to provide a method for easily manufacturing a highly reliable laminated ceramic capacitor.

[0005]

The present invention for achieving the above-mentioned first object is to provide a dielectric porcelain, a first internal electrode layer embedded in the porcelain, and a porcelain embedded in the porcelain. A second internal electrode layer having a region facing the first internal electrode layer, and the first internal electrode layer provided on the outer peripheral surface of the porcelain and the first internal electrode layer.
A multilayer ceramic capacitor comprising a first external electrode layer connected to the internal electrode layer of and a second external electrode layer provided on the outer peripheral surface of the porcelain and connected to the second internal electrode layer, The present invention relates to a laminated porcelain capacitor in which the diameter of crystal grains in a region adjacent to the first and second external electrode layers of the porcelain is smaller than the diameter of crystal grains in other regions. The present invention for achieving the above second object is to provide an unfired dielectric porcelain, a first unfired internal electrode layer embedded in the unfired dielectric porcelain, and the unfired dielectric. Forming a laminated green chip having a second unfired internal electrode layer embedded in a body porcelain and having a region facing the first unfired internal electrode layer; and a conductive material. Of a conductive paste containing the above powder, a grain growth inhibitor and an organic binder is applied to the first and second regions of the outer peripheral surface of the laminated raw chip so as to be connected to the first and unfired internal electrode layers. To form first and second unfired external electrode layers and firing the laminated green chip having the first and second unfired external electrode layers. It relates to a manufacturing method.

[0006]

[Operation and effect] First and second aspects of the first invention
The small crystal grain region in the vicinity of the external electrode layer has relatively large mechanical strength. Therefore, cracks are less likely to occur even when thermal shocks such as solder are applied to the first and second external electrode layers. Since the region between the first and second internal electrode layers is a relatively large crystal grain, a relatively large capacitance can be obtained. In the second invention, the grain growth suppressing substance diffuses into the porcelain layer during firing,
It is possible to prevent the crystal diameter in the vicinity of the external electrode layer from increasing. Thereby, the laminated ceramic capacitor specified in the first aspect of the invention can be easily obtained.

[0007]

[First Embodiment] First, (Ba 0.90 Ca 0.06 Sr
0.04 ) (Ti 0.82 Zr 0.18 ) O 3 with respect to 99% by weight of the main component of the porcelain, Li 2 O-BaO-CaO-Sr
A dielectric ceramic material was prepared in which 1% by weight of a glass component composed of O—SiO 2 was added.

Next, an organic binder, a dispersant, and an antifoaming agent were mixed with this dielectric ceramic material to prepare a slurry. Next, using this slurry, the thickness of 4
A plurality of 0 μm green sheets (unfired porcelain sheets, that is, porcelain green sheets) were prepared.

Next, a conductive paste containing Ni (nickel) particles and an organic binder was printed in a predetermined pattern on a plurality of green sheets. Next, 40 green sheets are laminated so that the first and second internal electrode layers facing each other are formed, and further, 5 green sheets not coated with the conductive paste are laminated on the upper and lower sides thereof, respectively. By thermocompression bonding and cutting into a desired shape, a laminated raw chip 10 as shown in FIG. 1 was obtained. The laminated green chip 10 is composed of a green ceramic 11 and first and second green internal electrode layers 12 and 13 embedded in the green ceramic 11.

Next, in order to form an external electrode layer, Ni is used.
A conductive paste for an external electrode was prepared, which was composed of 100 parts by weight of (nickel) powder, 10 parts by weight of Dy 2 O 3 (dysprosium oxide), and 30 parts by weight of an organic binder. next,
A conductive paste for external electrodes was applied to both end faces of the laminated green chip 10 by a dipping method to form the first and second unsintered external electrode layers 14 and 15 shown in FIG. The first and second unsintered external electrode layers 14 and 15 are connected to the first and second unsintered internal electrode layers 12 and 13, respectively.

Next, the one shown in FIG.
Sintered porcelain 21 shown in FIG. 2 after being fired at 150 ° C. for 2 hours
And the first and second internal electrode layers 22 and 23 embedded in the porcelain 21 and the first and second outer peripheral surfaces of the porcelain 21.
To obtain a laminated porcelain capacitor including the external electrode layers 24 and 25. The porcelain 21, the first and second inner electrode layers 22 and 23, and the first and second outer electrode layers 24 and 25 shown in FIG.
Is the unfired porcelain 11, the first and second unfired inner electrode layers 12 and 13, and the first and second unfired outer electrode layers 1 of FIG.
It is formed based on Nos. 4 and 15.

In this firing step, Dy 2 O 3 as a grain growth suppressing substance contained in the unfired first and second external electrode layers 14 and 15 diffuses into the porcelain 11. As a result, as shown schematically in FIG.
Small particle size porcelain regions 21a are formed in the vicinity of the first and second outer electrode layers 24 and 25, respectively, which are formed by baking the unsintered outer electrode layers 14 and 15. This small particle size porcelain region 21a
The diameter of the crystal particles of 1 was 1-2 when observed with an electron microscope.
It was μm, which was smaller than the diameter (about 5 μm) of the crystal grains in another region 21b such as between the first and second internal electrode layers 22 and 23. Further, the depth from the surface of the small particle size porcelain region 21a was about 20 μm. The small particle size porcelain regions 21a near the first and second external electrode layers 24 and 25 have relatively high mechanical stability and are resistant to thermal shock. On the other hand, the inner region 21b has a relatively large particle size (about 5 μm) as in the conventional case.
Therefore, it is advantageous to obtain a large capacitance.

In order to confirm that the laminated ceramic capacitor of FIG. 2 is strong against thermal shock, the laminated ceramic capacitor bonded on a glass epoxy substrate is immersed in a solder bath at 350 ° C. for 5 seconds without preheating. Porcelain after pulling up
The surface of the porcelain was polished to confirm the presence or absence of cracks in the porcelain 21. When this soldering resistance test was conducted on 50 laminated ceramic capacitors, the number of cracks generated was zero.
For comparison, the first and second unsintered external electrode layers 14,
A laminated ceramic capacitor was manufactured by the same method as in Example except that Dy 2 O 3 was not included in 15, and cracks were confirmed by the same method. As a result, 5 out of 50 cracks were found. When a similar test was conducted with the temperature of the solder bath at 400 ° C., one of 50 cracks was found in this example, and 32 of 50 cracks were found in the conventional example. Further, when a similar test was conducted with the temperature of the solder bath set to 300 ° C., no crack was observed in any of the present example and the conventional example. Note that the capacitance,
Regarding electrical characteristics such as tan δ, there was no substantial difference between this example and the conventional example.

[0014]

Second Example Next, in order to confirm that the amount of Dy 2 O 3 added to the first and second unsintered external electrode layers 14 and 15 can be changed, the amount of Dy 2 O 3 added Was changed to 5 parts by weight and 20 parts by weight, and a laminated ceramic capacitor was manufactured by the same method as in the first embodiment, and crack generation due to solder was examined by the same method. No. of 50 cracks were generated by immersion in a solder bath at 300 ° C. and 350 ° C. Also, 40
At 0 ° C., 6 out of 50 cracks occurred.
In case of 20 parts by weight, 300 ° C, 350 ° C, 400
The number of cracks in 50 cracks was 0 at any temperature. When the amount of the grain growth inhibitor is less than 5 parts by weight, the effect of inhibiting the grain growth cannot be obtained remarkably, and when it exceeds 20 parts by weight, the resistance of the electrode increases. Therefore, it is desirable to limit the grain growth inhibitor to 20 parts by weight or less.

[0015]

[Third Example] Next, in order to confirm that a grain growth inhibitor other than Dy 2 O 3 can be used,
5 parts by weight of Y 2 instead of Dy 2 O 3 in the examples
O 3 (yttrium oxide), 5 parts by weight of Nd 2 O 3 (neodymium oxide), 10 parts by weight of Sm 2 O 3 (samarium oxide), 10 parts by weight of Er 2 O 3 (erbium oxide), 1
0 parts by weight of Yb 2 O 3 (ytterbium oxide), and 1
Six kinds of laminated ceramic capacitors were prepared in the same manner as in the first embodiment except that 0 part by weight of Gd 2 O 3 (gadolinium oxide) was added.
The occurrence of cracks was examined by immersing 50 pieces in each of the solder baths at ℃ and 400 ℃. As a result, at 300 ° C. and 350 ° C., the number of cracks generated was 0 in all of the six types of laminated ceramic capacitors. In the case of 400 ° C., Y 2 O 3 is 4, Nd 2 O 3 is 5, Sm 2 O 3 is 2, Er 2 O 3 is 0, Yb 2 O 3 is 1, Gd 2 O
It was 2 in 3 .

[0016]

MODIFICATION The present invention is not limited to the above-described embodiments, and the following modifications are possible, for example. (1) First and second internal electrodes 22, 23, and first
If the second external electrodes 24 and 25 are formed of a base metal paste such as Ni, the cost can be reduced. However, another conductive paste made of Pd, Ag, Cu or a combination thereof is used. It can also be formed. When a noble metal paste is used, firing in an oxidizing atmosphere is possible, so the porcelain material can be changed to one that is fired in an oxidizing atmosphere. (2) The grain growth suppressing substance may be a rare earth oxide other than the substances shown in the first to third embodiments or another metal oxide (for example, zirconium oxide). (3) The composition of the porcelain can be various compositions other than those in the examples. For example, in the examples, the main site A contains barium, calcium and strontium, and the B site contains titanium and zirconium. However, the A site is one of three or any two, and the B site is titanium. can do. The firing temperature can also be changed to, for example, 1100 to 1400 ° C. according to the change in the composition of the porcelain material. Also, the composition of the glass component can be changed.

[Brief description of drawings]

FIG. 1 is a sectional view showing a part of a laminated green chip according to an embodiment of the present invention.

FIG. 2 is a sectional view schematically showing a part of the laminated ceramic capacitor of the example.

FIG. 3 is a sectional view showing a part of a conventional laminated ceramic capacitor.

[Explanation of symbols]

 21a small particle size region 21b large particle size region 22,23 first and second internal electrodes 24,25 first and second external electrodes

Claims (2)

[Claims]
1. A second interior having a dielectric porcelain, a first internal electrode layer embedded in the porcelain, and a region embedded in the porcelain and facing the first internal electrode layer. An electrode layer, a first outer electrode layer provided on the outer peripheral surface of the porcelain and connected to the first inner electrode layer, and an outer layer provided on the outer peripheral surface of the porcelain and connected to the second inner electrode layer And a second external electrode layer formed on the porcelain, the diameter of crystal grains in a region adjacent to the first and second external electrode layers of the porcelain is larger than the diameter of crystal grains in other regions. A laminated porcelain capacitor characterized by being small.
2. An unfired dielectric porcelain, a first unfired internal electrode layer embedded in the unfired dielectric porcelain, and a first unfired dielectric porcelain embedded in the unfired dielectric porcelain. A step of forming a laminated green chip having a second unsintered internal electrode layer having a region facing the unsintered internal electrode layer; a powder of a conductive material, a grain growth inhibitor and an organic binder; And a first and second unbaked conductive paste containing a conductive paste containing: is applied to the first and second regions of the outer peripheral surface of the laminated raw chip so as to be connected to the first and unbaked internal electrode layers. And a step of firing the laminated green chip having the first and second unfired external electrode layers, the method of manufacturing a laminated ceramic capacitor.
JP31408991A 1991-10-31 1991-10-31 Multilayer ceramic capacitor and method of manufacturing the same Expired - Fee Related JP2945529B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP31408991A JP2945529B2 (en) 1991-10-31 1991-10-31 Multilayer ceramic capacitor and method of manufacturing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP31408991A JP2945529B2 (en) 1991-10-31 1991-10-31 Multilayer ceramic capacitor and method of manufacturing the same

Publications (2)

Publication Number Publication Date
JPH05129152A true JPH05129152A (en) 1993-05-25
JP2945529B2 JP2945529B2 (en) 1999-09-06

Family

ID=18049109

Family Applications (1)

Application Number Title Priority Date Filing Date
JP31408991A Expired - Fee Related JP2945529B2 (en) 1991-10-31 1991-10-31 Multilayer ceramic capacitor and method of manufacturing the same

Country Status (1)

Country Link
JP (1) JP2945529B2 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007123389A (en) * 2005-10-26 2007-05-17 Kyocera Corp Laminated electronic component
JP5462962B1 (en) * 2013-01-31 2014-04-02 太陽誘電株式会社 Multilayer ceramic capacitor
JP2014150240A (en) * 2013-11-19 2014-08-21 Taiyo Yuden Co Ltd Multilayer ceramic capacitor
JP2014204117A (en) * 2013-04-08 2014-10-27 サムソン エレクトロ−メカニックス カンパニーリミテッド. Multilayer ceramic capacitor and method of manufacturing the same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007123389A (en) * 2005-10-26 2007-05-17 Kyocera Corp Laminated electronic component
JP5462962B1 (en) * 2013-01-31 2014-04-02 太陽誘電株式会社 Multilayer ceramic capacitor
US20140211367A1 (en) * 2013-01-31 2014-07-31 Taiyo Yuden Co., Ltd. Multilayer ceramic capacitor
US9177726B2 (en) * 2013-01-31 2015-11-03 Taiyo Yuden Co., Ltd. Multilayer ceramic capacitor
JP2014204117A (en) * 2013-04-08 2014-10-27 サムソン エレクトロ−メカニックス カンパニーリミテッド. Multilayer ceramic capacitor and method of manufacturing the same
US9030801B2 (en) 2013-04-08 2015-05-12 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic capacitor and method of manufacturing the same
JP2014150240A (en) * 2013-11-19 2014-08-21 Taiyo Yuden Co Ltd Multilayer ceramic capacitor

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Publication number Publication date
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