TW527607B - Ceramic electronic element - Google Patents

Abstract

The present invention relates to a ceramic electronic element. The object of the present invention is related to a ceramic electronic component that does not contain Pb components, quickens the sintering of a ceramic element body, is improved in adherence strength and humidity resistance, and at the same time, uses a conductive paste for suppressing the abnormal heat generation in the ceramic element body to form a terminal electrode. The present ceramic electronic component has a ceramic element body, and a terminal electrode formed on the ceramic element body using a conductive paste. The conductive paste contains a conductive constituent, glass powder, and an organic vehicle. The glass powder contains crystallization glass. The crystallization glass is an oxide made of B, Bi, and Al constituents, alkaline earth metal, and inevitable impurities. At least one portion of the glass powder is fused for penetrating into the ceramic body, when the terminal electrode is to be baked for forming, and the depth in the penetration is set to be within 150 mum from the surface of the ceramic body.

Description

V. Description of the Invention (ii) The present invention relates to ceramic and electronic components used in medium and high-voltage batteries, and particularly to ceramic capacitors used in medium and high voltage regions. Taurman electronic parts are traditionally ceramics made of Taurman materials such as dielectric f, semiconductors, and piezoelectric bodies. The electrodes and wiring materials attached to these Taojing electronic parts often use conductive paste. The conductive paste used when forming the electrodes of Taunman electronic parts may be broken glass powder. The effect of adding glass powder to the conductive paste is that it softens and flows when the electrode is sintered, thereby promoting the sintering of the conductive components and improving the connection strength of the terminal 2 'Using glass to cover the ceramic body can improve the wet performance; The electronic component is a pseudocapacitor material, which can fill the gap generated on the interface surface of the ceramic body of the terminal pad to prevent the capacitance from decreasing. ^ / In addition, the conductive paste used in the formation of electrodes for ceramics has been using the wrong glass. However, in recent years, due to environmental concerns, the use of non-lead glass has been required. Brief description of the invention However, the ceramic electronic parts used in the middle and high voltage areas of the terminal electrodes are formed by using the existing conductive paste added with non-lead glass, such as bismuth glass, especially the ceramic capacitors used in the middle and high voltage areas and Compared with the same ceramic electronic component in which the conductive paste forms the terminal electrode, there is a problem that the heating temperature of the ceramic body is higher. This is considered to be due to the fact that the secret component in the glass diffuses to the ceramic body under high voltage and high-frequency load, and Taoman is reduced to cause semiconductorization, so that the tan 6 of the ceramic body rises. 527607 A7

527607 A7 B7 V Description of the invention (3) The content of the crystallized glass is 1 to 25% by volume. The ceramic electronic component of the present invention is the above-mentioned ceramic electronic component, which is characterized in that the ceramic electronic component is a ceramic capacitor used in a medium to high voltage region. Brief Description of the Drawings Fig. 1 is a sectional view of a ceramic electronic component according to an embodiment of the present invention. Component number indication 1 ceramic electronic component 2 ceramic body 3 terminal electrode Detailed description of the invention The ceramic electronic component of the present invention requires the terminal electrode to include crystallized glass composed of boron, aluminum, aluminum, and earth metal. That is, it is required to solidify a conductive paste containing the crystallized glass to form a terminal electrode. Moreover, it is required that such crystallized glass be dazzled when solidified to form a terminal electrode, and penetrate into the ceramic body, and the penetration depth is less than 150 micrometers from the surface of the ceramic body. In this way, the ceramic electronic component of the present invention does not contain a lead component, can promote sintering of the ceramic body, improve joint strength, and improve moisture resistance, and can also suppress abnormal heat generation of the ceramic body, thereby suppressing a rise in tan δ of the ceramic body. As an unavoidable impurity, it may be desirable to contain trace amounts of other elements. The so-called crystallized glass of the present invention refers to an amorphous glass obtained when the glass is manufactured, but at least a part of the glass is crystallized by further heating. The crystalline melting temperature is a temperature at which the crystallized glass starts to melt when the glass is heated. In addition, the so-called curing temperature -6-this paper size is applicable _ National Standard (CNS) A4 size (210 X 297 mm)

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Line 527607 A7 B7 5. Description of the invention (4) Degree refers to the temperature when the conductive component is sintered after the conductive paste is coated on the ceramic body. In the case of conductive paste for forming terminal electrodes of ceramic electronic parts, the ratio is usually used. The melting point of the conductive component is 100 to 200 lower. (It is cured at a temperature of about 3. The alkaline earth metal component contained in the conductive paste used to form the terminal electrode of the ceramic electronic component of the present invention can be selected from Ca, Sr, and Ba. However, it is convenient for handling when manufacturing glass. In consideration of environmental protection, it is preferable to use Ca or Sr. Also, the content of the crystallized glass contained in the conductive paste used to form the terminal electrode of the ceramic electronic component of the present invention is preferably relative to 100% by volume. The conductive component and the content of the crystallized glass contained in the conductive paste are vol.%. When the added amount is less than 1 vol.%, The effect of including the crystallized glass is small. It is difficult to ensure the bonding strength of the terminal electrode. , The proportion of glass penetration in the ceramic body increases. If it is used in the medium and high voltage area, the ceramic body will generate abnormal heat, and at the same time, the glass will segregate on the surface of the terminal electrode, resulting in the situation that the solder is not easy to wet or the plating is not good. Yes, the conductive paste included in the conductive paste used to form the terminal electrode of the ceramic electronic component of the present invention The composition is not particularly limited, and it is possible to appropriately adjust and use precious metal powders such as Ag, Pd, alloy powders of these metals, base metal powders such as Ni, Cu, and alloy powders of these metals. The present invention is described below with reference to a ceramic capacitor as an example. An embodiment of a ceramic electronic component will be described in detail. A ceramic capacitor includes a ceramic body 2 and a pair of terminals are formed on the two main surfaces of the ceramic body 2 with the conductive paste of the present invention. CNS) A4 size (210X297 mm)

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Line 527607 A7 ______B7 V. Description of the invention (5 ^) Electrodes 3, 3, leads 4, 4 electrically connected to the terminal electrodes 3, 3, solder 5 which electrically connects the terminal electrodes 3, 3 to the leads 4, 4 and is mechanically connected 5 5 and 5. Encapsulating resin 6 formed by completely covering the ceramic body 2, the terminal electrodes 3 and 3 and the solders 5 and 5 and covering one end of the leads 4 and 4. The Taumann body 2 is made of a material that functions as, for example, a dielectric, a magnet, a piezoelectric body, an insulator, or the like, and is formed by sintering a single-plate or laminated Tauman body, but the ceramic electronic part of the present invention The ceramic body is not particularly limited to these. The terminal electrodes 3 and 3 are composed of the conductive paste of the present invention described above, and are formed, for example, by coating and drying the two main surfaces of a ceramic body, followed by sintering. For the terminal electrodes 3 and 3, the conductive paste of the present invention may be applied to both main surfaces of the green ceramic body before sintering to form an electrode film and sintered simultaneously with the green tantalman body. There is no particular limitation on the formation method. . . The ceramic electronic component of the present invention is not limited to the shape of the ceramic capacitor shown in FIG. 1. For example, the ceramic electronic component may include a ceramite body formed by sintering a ceramic body laminated with a plurality of unsintered ceramic sheets, and the ceramic body A laminated ceramic electronic component of a pair of terminal electrodes formed on the two main surfaces of the body with the conductive paste of the present invention. The material of the bow wire and the material of the sealing resin are not particularly limited, and they may not be provided. Example t The shout capacitor shown in Fig. 1 was fabricated, and the heating temperature was measured. First, according to the various compositions shown in Table 1, the alkaline earth metal oxides B1203, HsB03, Al (OH) 3'CaC03, SrC03, and aC0,3 were prepared as raw materials, and placed in a platinum crucible. Keep the pot at 900 ~ 1300 ° C for 1 hour. Then -8-t X 297 ^)-527607 A7 B7 V. Description of the invention (6) After confirming that the sample is completely melted, take it out of the furnace and put it into pure water to vitrify it. The obtained glass beads were wet-pulverized by a ball mill method, and glass powders of samples 1 to 9 having a composition ratio shown in Table 1 were obtained. For the glass powders of samples 1 to 6, it was confirmed from the DTA curve and high-temperature X-ray analysis that if the temperature was further increased, crystallized glass was formed, and the glass powders of samples 7 to 9 were confirmed to be amorphous glass. Table 1 Composition of sample glass frit B2O3 (mol%) Bi203 (mol%) ai2o3 (mol%) MO (M = Ca 'Sr, BaXmol%) 1 B-Bi-Al-Ca-0 Crystallization 30 28 7 35 2 35 5 30 3 B-Bi-Al-Sr-0 28 7 35 4 35 5 30 5 B-Bi-Al-Ba-0 28 7 35 6 35 5 30 7 B-Bi-Al-Ca-0 Amorphous State 50 20 8 22 8 B-Bi-Al-Sr-0 9 B-Bi-Al-Ba-0 Next, as a conductive component, 33% by volume of Ag powder having a particle size of 0.1 to 5 microns, and samples 1 to 9 6% by volume of glass powder and 61% by volume of excipient were mixed and ground with a three-roll mill to obtain conductive pastes of samples 1 to 9. As the excipient, a solution prepared at a ratio of 80% by weight of terpineol and 20% by weight of ethyl cellulose was used. Next, the conductive pastes of samples 1 to 9 were screen-printed on a 3 mm diameter stencil on both main surfaces of a ceramic body made of barium titanate with a target capacitance of InF, and 800 ° C in air for 2 hours. The conditions are sintered to form the terminal electrode. -9- This paper rule ^ Applies to China National Standard (CNS) A4 specifications (210X297 Public Love 527 607 A7 B7 __ V. Description of the invention (7) Make test samples 1 to 9 each for 200 Here, the depth of infiltration of glass from the surface of the ceramic body was measured for 100 samples of 1 to 9 test samples, and the measurement results are summarized in Table 2. The penetration depth of glass was measured by X-ray micro-analysis method. The measurement conditions were an acceleration voltage of 15 kV, an irradiation current of 100 nA, and a time lag (Dwell time) of 50 ms. Then, the remaining 1 to 9 test samples of each of the 100 samples were tested. Lead wires were soldered to the terminal electrodes, and the ceramic body, the terminal electrodes, and one end of the lead wires were covered with a sealing resin to obtain ceramic capacitors of samples 1 to 9. Here, an AC voltage of 3 kVp-p was applied to the ceramic capacitors of samples 1 to 9, and Thermocouple measurement package The temperature of the fat surface was determined as the difference (△ T) from 25 ° C to room temperature and summarized as the heating temperature in Table 2. The evaluation method was to use samples with heating temperature below 30 ° C as the range in accordance with the present invention. The samples are marked with 0, and the samples with a heating temperature of 30 ° C or more are regarded as samples that do not meet the scope of the present invention, and marked with X. Table 2

Depth of penetration of the sample from the ceramic surface (micron) Heating temperature Δ CC -10- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 527607

~~-~~ — ^ ~ EZ ~ 40.5 I x ~ As shown in Table 2, as the crystallized glass, at least one selected from the group consisting of B, 、, A, and Ca = Sr, Ba as the alkali = metal. A ceramic capacitor of samples 1 to 6 containing glassy powders of samples 1 to 6 has a penetration depth less than that! For the ceramic capacitors of samples 50 and 50, the heating temperature (ΔΤ) was 21.5 to 24.5. (:, Within the scope of the present invention. The ceramic capacitors of samples 2, 4, and 6 with penetration depths exceeding 150 // m to reach 173 to 189 // m have a heating temperature of 36 9 to 38 cavities. Outside the range, it is composed of B, Bi, A1 and at least _ selected from the group consisting of ~, Sr ^ Ba as the soil test metal, but contains samples 7 to 9 as amorphous glass The ceramic capacitors of glass powder samples 7 to 9 all penetrate more than 150 micrometers and reach 20.5 to 25 micrometers. Therefore, the heating temperature is 38.5 to 40.5 ° C, which is outside the scope of the present invention. As described above, the ceramic electronic part of the present invention is characterized by including a ceramic body and a terminal electrode for forming an electric paste on the shout body. As the ceramic electronic part, the conductive paste includes a conductive component, glass powder, and an organic compound. Opening agent, the glass powder contains crystallized glass. Crystallized glass is an oxide composed of B, Bi, A1, alkaline earth metal and unavoidable impurities. At least a part of the glass breaks when it is solidified to form a terminal electrode. Penetrates into the ceramic body, The penetration depth is less than 15 micrometers from the surface of the ceramic body. Even in the case of medium and high voltage areas, it can provide the S junction that can promote the ceramic body, improve the joint strength, improve the moisture resistance, and can also suppress the Taoman-11 -This paper size applies to China National Standard (CNS) A4 (210X 297mm)

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527607 A7 B7 V. Description of the invention (9) The ceramic electronic parts that do not contain lead in terminal electrodes are abnormally hot. In addition, if the content of the crystallized glass contained in the conductive paste used when the terminal electrode of the ceramic electronic component of the present invention is cured is formed, the content of the crystallized glass contained in the conductive paste is 1 to 100% by volume of the conductive component. 25% by volume. It can promote the sintering of the ceramic body, improve the bonding strength of the terminal electrode, improve the humidity resistance, and at the same time suppress the abnormal heating of the ceramic body. At the same time, when using this conductive paste to form the terminal electrode, it can improve the suppression of the glass in the terminal electrode. The effect of surface segregation and solder infiltration and plating failure. -12- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

527607 Patent Application No. 091101126 Replacement Patent Scope (January 1992) Scope A8 B8 C8 D8 1. A ceramic electronic component comprising a ceramic body and a terminal electrode formed on the ceramic body by a conductive paste, characterized in that the conductive paste contains a conductive component, glass powder, and an organic excipient; The glass powder contains crystallized glass; the crystallized glass is an oxide composed of boron, bismuth, aluminum, alkaline earth metals, and unavoidable impurities; at least a part of the glass powder melts and penetrates into the ceramic body when solidified to form the terminal electrode Inside; and the penetration depth of the penetration is less than 150 microns from the surface of the ceramic body. 2. The ceramic electronic component according to item 1 of the scope of patent application, wherein the alkaline earth metal included in the conductive paste is at least one selected from the group consisting of Ca, Sr, and Ba. 3. The ceramic electronic component according to item 1 or 2 of the patent application scope, characterized in that the content of the crystallized glass contained in the conductive paste is 1 to 25% by volume relative to 100% by volume of the conductive component. 4. The ceramic electronic component according to item 1 of the scope of patent application, characterized in that the ceramic electronic component is a ceramic capacitor used in a medium-high voltage region. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)