JP2006202857A - Laminated ceramic electronic component and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated ceramic electronic component having an outer electrode whose adhesion strength with a ceramic element is large and which is superior in density, and to provide a manufacturing method of the laminated ceramic electronic component which can efficiently manufacture the laminated ceramic electronic component. <P>SOLUTION: A material which comprises a conductive component and a ceramic component and in which the ceramic component comprises ceramic material powder and sintering acid [A] is used as an outer electrode forming material. A material comprising a dielectric ceramic component (powder) and sintering acid [B] is used as a dielectric ceramic layer forming material. A rate: C<SB>A</SB>/C<SB>B</SB>of the content C<SB>A</SB>(weight%) of the sintering agent [A] in the ceramic component and the content C<SB>B</SB>(weight%) of the sintering agent [B] in the dielectric ceramic layer forming material is set so that it satisfies a formula: 1<C<SB>A</SB>/C<SB>B</SB>≤3. The non-calcined ceramic elements formed by using the dielectric ceramic layer forming material, the outer electrode forming material and an inner electrode forming material are simultaneously and integrally calcined. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a multilayer ceramic electronic component and a method for manufacturing the same, and more specifically, has a structure in which an external electrode is provided on the surface of a multilayer ceramic element in which a dielectric ceramic layer and an internal electrode are stacked, and the dielectric ceramic. Multilayer ceramic electronic component manufactured through a step of simultaneously and integrally firing unsintered multilayer ceramic elements formed using a layer forming material, an external electrode forming material, and an internal electrode forming material, and its manufacture Regarding the method.

  For example, as shown in FIG. 3, a surface-mounted multilayer ceramic capacitor, which is one of representative electronic components, includes a plurality of internal electrodes 52a and 52b in a ceramic element (electronic component element) 51 made of a dielectric. Are laminated and disposed via the ceramic layer 53, and the internal electrodes 52a and 52b facing each other via the ceramic layer 53 are alternately drawn out to the end faces 54a and 54b on the opposite side of the ceramic element 51, and the ceramic element 51 has a structure connected to a pair of external electrodes 55a and 55b formed on both end faces (Patent Document 1).

  In the multilayer ceramic capacitor 50, the external electrodes 55a and 55b include first terminal electrodes 56a and 56b, second terminal electrodes 57a and 57b formed thereon, and nickel plating layers 58a and 58b formed thereon. 58b and solder plating layers 59a and 59b formed thereon.

  In the multilayer ceramic capacitor 50, in order to improve the adhesion strength of the external electrodes 55a and 55b (the first terminal electrodes 56a and 56b constituting the external electrode) to the ceramic element 51, the first terminal electrodes 56a and 56b are provided with ceramics. In addition to including powder, the ceramic powder has the same composition as the dielectric constituting the ceramic element 51, and the particle diameter thereof is larger than the particle diameter of the dielectric constituting the ceramic element 51. The difference between the particle size of the dielectric material and the average particle size of the ceramic powder contained in the first terminal electrode is 0.2 μm to 1.0 μm, so that the sintering shrinkage of the external electrode is delayed, and the external electrode The timing of sintering shrinkage of the first terminal electrodes 56a and 56b is adjusted to match the timing of sintering shrinkage of the dielectric as much as possible. Tsu adhesion strength to click elements 51 large, the reliability of large external electrodes 55a, so that to form a 55b.

  However, in the conventional multilayer ceramic capacitor, the external electrodes 55a and 55b (the first terminal electrodes 56a and 56b constituting the external electrodes 55a and 56b) even when the difference in the average particle diameter is in the range of 0.2 μm to 1.0 μm. When the average particle size of the ceramic powder contained therein increases, the adhesion strength between the ceramic element 51 and the first terminal electrodes 56a and 56b increases, but the density (denseness) due to voids (pores) in the first terminal electrodes 56a and 56b. Degradation), and the sealing properties and moisture resistance of the external electrodes 55a and 55b are degraded.

On the other hand, even when the difference in average particle size is within the range of 0.2 μm to 1.0 μm, the average particle size of the ceramic powder contained in the external electrodes 55a and 55b (the first terminal electrodes 56a and 56b constituting the external electrodes 55a and 55b). When the diameter is reduced, the density (denseness) of the external electrodes 55a and 55b (the first terminal electrodes 56a and 56b constituting the external electrodes 55a and 55b) is increased and the sealing performance and moisture resistance are improved. There is a problem that the adhesion strength of 55b (the first terminal electrodes 56a and 56b constituting the same) is weakened.
Japanese Patent Laid-Open No. 10-144561

  The present invention solves the above-mentioned problems, and has a highly reliable multilayer ceramic electronic component provided with an external electrode having a high adhesion strength with a ceramic element and excellent in denseness, and efficiently producing the multilayer ceramic electronic component It is an object of the present invention to provide a method for manufacturing a multilayer ceramic electronic component that can be used.

In order to solve the above-mentioned problem, a method for manufacturing a multilayer ceramic electronic component of the present invention (Claim 1) includes:
A method for producing a multilayer ceramic electronic component having a structure comprising a multilayer ceramic element having a structure in which a dielectric ceramic layer and internal electrodes are laminated, and an external electrode formed on the surface of the multilayer ceramic element,
(a) A material containing a conductive component and a ceramic component as the external electrode forming material for forming the external electrode, wherein the ceramic component contains a ceramic material powder and a sintering aid [A]. Use
(b) As a dielectric ceramic layer forming material for forming the dielectric ceramic layer, a material containing a dielectric ceramic powder and a sintering aid [B] is used.
(c) content C _B (weight of content C _A (wt%), sintering aid of the dielectric ceramic layer forming material [B] of the sintering aid in ceramic component [A] %): C _A / C _{B is set} to a ratio that satisfies the requirement of the formula: 1 <C _A / C _B ≦ 3,
A step of simultaneously and integrally firing unfired multilayer ceramic elements formed using the dielectric ceramic layer forming material, the external electrode forming material, and the internal electrode forming material. It is a feature.

According to a second aspect of the present invention, there is provided a method for producing a multilayer ceramic electronic component according to the first aspect of the present invention, wherein the sintering aid [A] and the sintering aid [B] Is at least one selected from the group consisting of SiO ₂ , B ₂ O ₃ , and Li ₂ O.

  According to a third aspect of the present invention, there is provided a multilayer ceramic electronic component manufacturing method according to the first or second aspect of the present invention, wherein the conductive component constituting the external electrode is Ni, Cu, or Ag. It is characterized by being at least one selected from the group consisting of

  According to a fourth aspect of the present invention, there is provided a method for manufacturing a multilayer ceramic electronic component according to any one of the first to third aspects, wherein the external electrode is formed to form the external electrode. The ratio of the ceramic component in the material to the total amount of the conductive component and the ceramic component is in the range of 10 to 50% by weight.

The multilayer ceramic electronic component of the present invention (Claim 5)
A multilayer ceramic element having a structure in which a dielectric ceramic layer and an internal electrode are laminated; and an external electrode formed on a surface of the multilayer ceramic element, the dielectric ceramic layer forming material, A multilayer ceramic electronic component manufactured through a step of simultaneously and integrally firing unfired multilayer ceramic elements formed using the external electrode forming material and the internal electrode forming material,
(a) The external electrode contains a conductive component and a ceramic component, and the ceramic component contains a ceramic material and a sintering aid [A],
(b) The dielectric ceramic layer contains a dielectric ceramic material and a sintering aid [B],
(c) content C _B (weight of content C _A (wt%), sintering aid of the dielectric ceramic layer forming material [B] of the sintering aid in ceramic component [A] %) Ratio: C _A / C _B is characterized by satisfying the requirement of the formula: 1 <C _A / C _B ≦ 3.

The multilayer ceramic electronic component of claim 6 is the multilayer ceramic electronic component according to claim 5, wherein the sintering aid [A] and the sintering aid [B] are SiO ₂ , B It is characterized by being at least one selected from the group consisting of ₂ O ₃ and Li ₂ O.

  The multilayer ceramic electronic component according to claim 7 is the multilayer ceramic electronic component according to claim 5 or 6, wherein the conductive component constituting the external electrode is selected from the group consisting of Ni, Cu, and Ag. It is characterized by at least one kind.

  The multilayer ceramic electronic component according to claim 8 is the ceramic component in the external electrode forming material for forming the external electrode in the multilayer ceramic electronic component invention according to any one of claims 5 to 7. The ratio of the conductive component and the ceramic component to the total amount is in the range of 10 to 50% by weight.

A method for manufacturing a multilayer ceramic electronic component of the present invention (Claim 1) includes a multilayer ceramic element having a structure in which a dielectric ceramic layer and an internal electrode are laminated, and an external electrode formed on the surface of the multilayer ceramic element. (A) As an external electrode forming material, a conductive component and a ceramic component are included, and the ceramic component includes ceramic material powder and a sintering aid [A]. (B) A dielectric ceramic powder and a material containing a sintering aid [B] are used as a dielectric ceramic layer forming material, and (c) a sintering aid in the ceramic component is used. agent [a] of the content C _a (wt%), the proportion of the content of the sintering aid of the dielectric ceramic layer forming material _[B] C B (wt%): the C _a / C _B, 1 <C _A / C _B ≦ 3 In addition, the unfired multilayer ceramic element formed using the dielectric ceramic layer forming material, the external electrode forming material, and the internal electrode forming material is fired simultaneously and integrally. Therefore, it is possible to efficiently produce a multilayer ceramic electronic component having a high adhesion strength with a ceramic element, having an external electrode excellent in denseness, and having good characteristics.

Incidentally, the sintering aid [A] of the content C _A (wt%), the proportion of content C _B (wt%) of the sintering aid [B]: the _{C A / C B, 1 <} C A The ratio satisfying the requirement of / C _B ≦ 3 is that when C _A / C _B is 1 or less, the terminal strength (adhesion strength of the external electrode) becomes insufficient, and the moisture resistance tends to decrease. If C _A / C _B exceeds 3, for example, in the case of a multilayer ceramic capacitor, there is a problem that the capacitance change rate becomes too large to obtain a multilayer ceramic capacitor having desired characteristics. It depends.

  When a ceramic component (powder) having the same or substantially the same composition as the dielectric ceramic constituting the multilayer ceramic element is used as the ceramic component constituting the external electrode forming material, the ceramic constituting the external electrode forming material Even when the component diffuses into the dielectric ceramic that constitutes the multilayer ceramic element, the electrical characteristics of the dielectric ceramic are not deteriorated, so the external electrode has high adhesion strength with the ceramic element and excellent compactness. In addition, it is possible to efficiently manufacture a monolithic ceramic electronic component having good electrical characteristics.

Further, a sintering aid [A] of the content C _A (wt%), the proportion of the sintering aid [B] of the content C _B (wt%): ratio of C _A / C _B, the calcination step It does not change substantially even after going through.

In addition, as in the method for manufacturing a multilayer ceramic electronic component according to claim 2, in the structure of the method for manufacturing a multilayer ceramic electronic component according to claim 1, the sintering aid [A] and the sintering aid [B] By using at least one selected from the group consisting of SiO ₂ , B ₂ O ₃ , and Li ₂ O, an external electrode forming material (a ceramic component constituting the material) and a dielectric ceramic layer forming material ( It is possible to efficiently and surely sinter the dielectric ceramic constituting the ceramic element to form a dense external electrode having high adhesion strength to the ceramic element.

  Further, as in the method of manufacturing a multilayer ceramic electronic component according to claim 3, by using at least one selected from the group consisting of Ni, Cu, and Ag as the conductive component constituting the external electrode, the electrical connection with the internal electrode is achieved. It is possible to form an external electrode that is excellent in reliability, is dense, and has high adhesion strength to the ceramic element.

Further, the ratio of the ceramic component in the external electrode forming material for forming the external electrode to the total amount of the conductive component and the ceramic component as in the method for manufacturing a multilayer ceramic electronic component according to claim 4 is 10 to 50 weights. By setting the ratio in the range of%, it is possible to reliably form an external electrode that is excellent in conduction reliability with the internal electrode, is dense, and has high adhesion strength to the ceramic element.
In addition, the ratio of the ceramic component is set in the range of 10 to 50% by weight as described above. When the ceramic component ratio is less than 10% by weight, the sintering of the external electrode is compared with the sintering shrinkage of the dielectric. This is because the shrinkage starts at a lower temperature, which causes a mismatch in the sintering shrinkage, resulting in external electrode claps. When it exceeds 50% by weight, the sintering of the external electrode is compared with the sintering shrinkage of the dielectric. Since the shrinkage starts at a higher temperature, the adhesion between the external electrode and the ceramic element is deteriorated and peeling occurs, and pores are generated in the external electrode itself, resulting in low density.

The multilayer ceramic electronic component of the present invention (Claim 5) has a structure including a multilayer ceramic element having a structure in which a dielectric ceramic layer and internal electrodes are laminated, and an external electrode formed on the surface of the multilayer ceramic element. And a laminate produced through a step of simultaneously and integrally firing unfired multilayer ceramic elements formed using a dielectric ceramic layer forming material, an external electrode forming material, and an internal electrode forming material A ceramic electronic component, wherein (a) the external electrode contains a conductive component and a ceramic component, and the ceramic component contains a ceramic material and a sintering aid [A], (b) a dielectric ceramic The layer contains a dielectric ceramic material and a sintering aid [B], (c) the content C _A (% by weight) of the sintering aid [A] in the ceramic component, and the dielectric ceramic layer Sintering in forming materials Agent ratio of content C _B (wt%) of _{[B]: C A / C} B has the formula: 1 <since meets the requirements of the C _A / C _B ≦ 3, adhesion between the ceramic element of external electrodes It is possible to obtain a multilayer ceramic electronic component that has high strength, is dense, and has high adhesion strength to a ceramic element.

Further, as in the multilayer ceramic electronic component of claim 6, the sintering aid [A] and the sintering aid [B] are at least one selected from the group consisting of SiO ₂ , B ₂ O ₃ and Li ₂ O. By using the seed, the external electrode forming material (ceramic component constituting the material) and the dielectric ceramic layer forming material (dielectric ceramic constituting the ceramic device) are surely sintered, and the dense ceramic device It is possible to obtain a highly reliable multilayer ceramic electronic component provided with an external electrode having a high adhesion strength to.

  Further, as in the multilayer ceramic electronic component of claim 7, by using at least one selected from the group consisting of Ni, Cu and Ag as the conductive component constituting the external electrode, the conduction reliability with the internal electrode is improved. It is possible to obtain a multilayer ceramic electronic component including an external electrode that is excellent and dense and has high adhesion strength to a ceramic element.

  The ratio of the ceramic component in the external electrode forming material for forming the external electrode to the total amount of the conductive component and the ceramic component as in the multilayer ceramic electronic component according to claim 8 is in the range of 10 to 50% by weight. By doing so, it becomes possible to obtain a multilayer ceramic electronic component having an external electrode that is excellent in conduction reliability with the internal electrode, is dense, and has high adhesion strength to the ceramic element.

  The features of the present invention will be described in more detail below with reference to examples of the present invention.

[Configuration of Multilayer Ceramic Electronic Component According to Embodiment of Present Invention]
FIG. 1 is a cross-sectional view showing a multilayer ceramic electronic component (a multilayer ceramic capacitor in this embodiment 1) according to an embodiment of the present invention.

  As shown in FIG. 1, the multilayer ceramic capacitor 10 includes a multilayer ceramic element (electronic component element) 1 made of a dielectric ceramic and a plurality of internal electrodes 2a and 2b stacked and disposed via a ceramic layer 3. In addition, a pair of internal electrodes 2 a and 2 b facing each other via the ceramic layer 3 are alternately drawn out to the opposite end faces 4 a and 4 b of the multilayer ceramic element 1 and formed on both end faces of the multilayer ceramic element 1. The external electrodes 5a and 5b are connected to each other.

  In this multilayer ceramic capacitor 10, Ni (nickel) plating layers 6a and 6b are disposed on the surfaces of the external electrodes 5a and 5b, and Sn (tin) plating is further provided on the Ni plating layers 6a and 6b. Layers 7a and 7b are formed.

[Production of Multilayer Ceramic Electronic Component According to Embodiment of Present Invention]
Next, a method for manufacturing the multilayer ceramic capacitor 10 will be described.

(1) First, with respect to the main component represented by the formula: 0.982Ba _1.015 TiO ₃ + 0.009Y ₂ O ₃ +0.009 (Mn _0.6 Ni _0.4 ) O, 0.21% by weight of MgO as a subcomponent, Ceramic green sheet for forming a dielectric ceramic layer using dielectric ceramic powder (dielectric material) having an average particle size of 0.3 μm and containing 0.38 wt% of SiO ₂ as a sintering aid [B] A conductive paste (Ni paste) containing Ni powder as a conductive component for forming Ni internal electrodes was printed on the substrate.

  (2) Then, by laminating the ceramic green sheets printed with the conductive paste, and laminating the ceramic green sheets for the outer layer not printed with the conductive paste on top and bottom of the ceramic green sheets, cutting them and applying barrel polishing As shown in FIG. 2A, an unfired multilayer ceramic element 1 (1a) in which the internal electrodes 2a and 2b were exposed on the end faces 4a and 4b was produced. The monolithic ceramic element 1 (1a) had a length of 4.0 mm, a width of 2.2 mm, and a height of 2.2 mm. 2A and 2B, the same reference numerals as those in FIG. 1 denote the same or corresponding parts.

(3) Next, as a ceramic component (powder) added to the external electrode forming material (conductive paste), the dielectric ceramic layer forming material (sintering aid) constituting the multilayer ceramic element (dielectric ceramic layer) [B] content of (SiO _2): in C _B 0.38 wt%) and the same composition, the ceramic powder having an average particle diameter of 0.1 to 1.0 [mu] m, as a sintering aid [a], A ceramic component (powder) containing SiO ₂ in a proportion as shown in Table 1 was prepared.

The ceramic components (powder) of sample numbers 1 to 8 in Table 1 are within the scope of the present invention.
Moreover, in Table 1, the ceramic components (powder) of sample numbers 9 to 14 marked with * in the sample numbers are outside the scope of the present invention. That is, in sample numbers 9, 10, 11, and 12, the content C _A (% by weight) of the sintering aid [A] in the ceramic component (powder) and the sintering aid in the dielectric ceramic layer forming material. Content ratio C _B (% by weight) of agent [B]: C _A / C _B exceeds the range of the present invention (exceeds 3 (times)). Content ratio C _A (wt%) of sintering aid [A] in (powder) and content C _B (wt%) of sintering aid [B] in the dielectric ceramic layer forming material : C _A / C _B is below the range of the present invention (below 1 (times)).

In Example 1, when the ceramic components (powder) of Sample Nos. 1 to 14 in Table 1 were prepared, the dielectric ceramic layer forming material (sintered) constituting the multilayer ceramic element (dielectric ceramic layer) Sintering aid [A] (SiO ₂ ) was added to auxiliary agent [B] (SiO ₂ ) content C _B : 0.38 wt%. For example, in the samples of Sample Nos. 1 to 14 in Table 1, the sintering aid is contained in the dielectric ceramic layer forming material in which the content of the sintering aid is included in the multilayer ceramic element (dielectric ceramic layer). After dispersing Si alkoxide in toluene / equinene so as to be 1, 2, 3, and 3.5 times the component ratio, the slurry is discharged, dried, heat-treated, and crushed. A ceramic component (powder) to be added to the external electrode was prepared.

(4) Then, the ceramic component (powder) prepared in the above (3) and the conductive component were mixed and dispersed to prepare a conductive paste (Ni paste) which is an external electrode forming material.
Specifically, the above ceramic component (powder) is added to Ni powder having a particle size of 0.5 μm at a ratio of nickel powder 52.6 wt% and ceramic component (powder) 22.6 wt%, A varnish composed of acrylic resin and terpineol was added so as to have a ratio of 24.8% by weight, and then mixed and dispersed using three rolls to prepare a Ni paste.

  (5) Next, as shown in FIG. 2 (b), the conductive paste (Ni paste) 15a (5a), 15b (5b) produced in the above (4) is used as an unfired multilayer ceramic element 1 (1a). The coating was applied to the end faces 4a and 4b from which the internal electrodes 2a and 2b were exposed, followed by heat treatment at 250 ° C. in the atmosphere for 5 hours to remove the binder.

  (6) After that, the multilayer ceramic element 1 after debinding is held in a reducing atmosphere at 1280 ° C. for 2 hours using a batch furnace capable of controlling the atmosphere, thereby forming the internal electrodes 2a and 2b and the multilayer ceramic element 1. The dielectric ceramic (layer) 3 and the Ni paste for forming external electrodes were fired simultaneously and integrally.

  (7) Next, the fired multilayer ceramic element is barrel-polished to remove the oxide film on the surface of the external electrodes 5a and 5b, and then Ni plating is performed on the external electrodes 5a and 5b to form Ni plated layers 6a and 6b. After the formation, Sn plating was further performed to form Sn plating layers 7a and 7b, thereby obtaining multilayer ceramic capacitors (samples 1 to 14 in Table 1) having the structure shown in FIG.

[Measurement of Characteristics of Multilayer Ceramic Electronic Component According to Embodiment of Present Invention]
The characteristics of the multilayer ceramic capacitor (sample) produced as described above were measured and evaluated by the following method.

(a) Terminal strength After attaching the lead wire to the external electrode provided with the Ni plating film and the Sn plating film using solder, it was necessary to pull the lead wire to peel the external electrode from the surface of the multilayer ceramic element. By measuring the magnitude of the force, the adhesion strength (terminal strength) of the external electrode to the multilayer ceramic element was examined.
In addition, about the terminal strength, the magnitude | size of the force required for peeling evaluated 0.6 kgf or more as favorable ((circle)), and less than 0.6 kgf was evaluated as bad (x).

(b) Moisture resistance characteristics Further, a moisture resistance load (85 ° C., 85%) test (100 samples) was performed to examine the moisture resistance characteristics.
As for the moisture resistance, 100 samples were examined by checking whether or not the plating solution entered after the moisture resistance load test, and those that did not allow the penetration of the plating solution were good (◯). Those in which the intrusion was observed were evaluated as defective (x).

(c) Design capacity characteristics The capacity change rate (ΔC / C ₂₀ ° C.) at −25 to 85 ° C., 1 V, and 1 KHz was measured, and the design capacity characteristics were examined.
Regarding design capacity characteristics, those with a capacity change rate (ΔC / C ₂₀ ° C) within ± 10% are evaluated as good design capacity characteristics (◯), and those exceeding ± 10% are designed capacity characteristics. Was evaluated as defective (x).
Table 1 also shows the evaluation results of the characteristics of the samples Nos. 1 to 14.

Content C _A (wt%) of sintering aid [A] in the ceramic component (powder) and content C _B (wt%) of sintering aid [B] in the dielectric ceramic layer forming material Ratio: In the case of sample numbers 1 to 8 in Table 1 where C _A / C _B is within the scope of the present invention, as shown in sample numbers 1, 3, 5, 7 and 2, 4, 6, 8, external It was confirmed that when the average particle size of the ceramic component (powder) contained in the electrode is increased, the terminal strength (adhesion strength) is increased and the moisture resistance is improved.
This is because, within the scope of the present invention, by increasing the addition amount of the sintering aid, the reactivity of the ceramic powder in the multilayer ceramic element and the ceramic component (powder) in the external electrode is increased, and the terminal strength ( This is because the adhesion strength of the external electrode) and moisture resistance are improved. From this result, by increasing the amount of the sintering aid in the ceramic component (powder) added to the external electrode, it is possible to improve the sealing performance as the external electrode while ensuring the mechanical strength of the external electrode. I understand that

In contrast, the content C _A (% by weight) of the sintering aid [A] in the ceramic component (powder) and the content C _{B of the} sintering aid [B] in the dielectric ceramic layer forming material. Ratio of (% by weight): In the case of samples Nos. 9 to 14 where C _A / C _B is out of the scope of the present invention, at least one of terminal strength (adhesion strength of external electrodes), moisture resistance characteristics, and design capacity characteristics It was confirmed that one characteristic was deteriorated and not preferable.
That is, as in sample No. 9-12, the content C _A of sintering aid [A], the ratio of content C _B (wt%) of the sintering aid [B]: the C _A / C _B In the case of samples exceeding the scope of the present invention (samples where C _A / C _B exceeds 3 (times)), the terminal strength is almost the same as when C _A / C _{B is set} to 3 (times), and the terminal strength (external The adhesion strength of the electrode) can be ensured, but the designed capacity change rate cannot be obtained.
This is considered to be caused by the amount of the sintering aid in the ceramic component (powder) added to the external electrode being excessive and the sintering aid being dissolved in the dielectric ceramic layer.

Further, as in sample numbers 13 to 14, the ratio of the content C _A of the sintering aid [A] and the content C _B (% by weight) of the sintering aid [B]: C _A / C _B In the case of a sample (C _A / C _{B is} 1 (times) or less) less than the range of the present invention, the terminal strength (adhesion strength of the external electrode) compared to the samples of sample numbers 1 to 8 within the range of the present invention ) Was low, and it was confirmed that the moisture resistance also deteriorated.

  A multilayer ceramic capacitor having a structure as shown in FIG. 1 (sample numbers 15 to 15 in Table 2) was obtained in the same manner as in Example 1 except for the sintering auxiliary agent added to the ceramic component (powder) in the external electrode. 17 samples) were prepared.

In Example 2, as the ceramic component (powder) added to the external electrode, the dielectric ceramic layer forming material (sintering aid [B]) constituting the multilayer ceramic element (dielectric ceramic layer) has an average particle size. Ceramic component (adding SiO ₂ , B ₂ O ₃ , Li ₂ O as sintering aids to 100.59 g of the same ceramic material as 0.3 μm of SiO ₂ containing 0.38 wt% (external electrode) ( The powder was prepared so that the ratio of the sintering aid to the whole powder was 1.5 times (additional sintering aid component: 0.19% by weight), dispersed in toluene / equinene, and the slurry was discharged. The ceramic component (powder) to be added to the external electrode was prepared by drying, heat treatment and crushing.

  And the characteristic was measured about the multilayer ceramic capacitor produced by forming an external electrode using the electrically conductive paste (Ni paste) which added the ceramic component (powder) produced as mentioned above. Table 2 shows the results.

  As shown in Table 2, when the sintering aids of Sample Nos. 15 to 17 in Table 2 different from Example 1 were used as the sintering aids contained in the ceramic component (powder), the above implementation was performed. It was confirmed that the same effects as those of Example 1 were obtained.

  Except for the sintering aid added to the ceramic component (powder) in the external electrode, the multilayer ceramic capacitor having the structure shown in FIG. Sample) was prepared.

In Example 3, as the ceramic component (powder) added to the external electrode, the dielectric ceramic layer forming material (sintering aid [B]) constituting the multilayer ceramic element (dielectric ceramic layer) has an average particle size. Sintering of the entire ceramic component (powder) added to the external electrode with SiO ₂ + Li ₂ O as a sintering aid in 100.59 g of the same ceramic material (including 0.38 wt% of 0.3 μm SiO ₂ ) Mixing so that the ratio of the whole auxiliary agent becomes 1.5 times (additional sintering auxiliary component: SiO ₂ : 0.10 wt%, Li ₂ O: 0.09 wt%), in toluene / equinene After dispersion, the slurry was discharged, dried, heat-treated, and crushed to produce a ceramic component (powder) to be added to the external electrode.

  And the characteristic was measured about the multilayer ceramic capacitor which formed the external electrode using the electrically conductive paste which added the ceramic component (powder) produced as mentioned above. Table 3 shows the results.

As shown in Table 3, as a sintering aid contained in the ceramic component (powder), lamination using the sintering aid (SiO ₂ + Li ₂ O) of Sample No. 18 in Table 3 different from Example 1 above. Also in the ceramic capacitor, it was confirmed that the same effect as the case of Example 1 was obtained.
In Example 3, two types of materials, SiO ₂ and Li ₂ O, are used as the sintering aid component. However, it is possible to use a combination of other sintering aid components. A combination of three or more types of sintering aid components is also possible.

  A multilayer ceramic capacitor having the structure as shown in FIG. 1 (sample of Table 4) is formed in the same manner as in Example 1 except for the dielectric ceramic layer forming material constituting the multilayer ceramic element (dielectric ceramic layer). Sample No. 19) was prepared.

In Example 4, as a dielectric ceramic layer forming material constituting the multilayer ceramic element (dielectric ceramic layer), the formula: 0.984Ba _1.010 TiO ₃ + 0.008Y ₂ O ₃ +0.008 (Mn _0.7 Ni _0.3 ) Dielectric ceramic powder containing 0.21% by weight of MgO as a subsidiary component and 0.26% by weight of SiO ₂ as a sintering aid component with respect to the main component represented by O (average particle size 0.3 μm) ) Was used.
And the characteristic was measured about the multilayer ceramic capacitor produced using the above-mentioned dielectric ceramic layer forming material. The results are shown in Table 4.

  As shown in Table 4, in the multilayer ceramic capacitor of Sample No. 19 in Table 4 manufactured using the above-mentioned dielectric ceramic powder, substantially the same effect as that of the sample of Sample No. 3 in Example 1 can be obtained. It was confirmed.

The dielectric ceramic layer forming material constituting the multilayer ceramic element (dielectric ceramic layer), the ceramic component (powder) added to the external electrode, and the conditions other than the firing temperature are the same as in Example 1 above. A multilayer ceramic capacitor (sample No. 20 in Table 5) having a structure as shown in FIG. 1 was produced.
That is, in this Example 5, with respect to the main component represented by CaZrO ₃ , 0.99% by weight of MnCO ₃ as an accessory component and 0.11% by weight of Li—Si glass as a sintering aid component Ni internal electrodes are printed on a ceramic green sheet made of a dielectric ceramic powder (dielectric material) (average particle size 0.3 μm), laminated, cut, and barrel-polished to form internal electrodes on both end faces. An exposed unfired multilayer ceramic element was produced.

Further, a material having the same composition as the dielectric ceramic layer forming material constituting the multilayer ceramic element (dielectric ceramic layer) (average particle size 0.3 μm, 0.11 weight of Li—Si glass as a sintering aid) 100 g) and the ratio of the sintering aid component contained in the ceramic component (powder) is a sintering aid contained in the dielectric ceramic layer forming material constituting the multilayer ceramic element (dielectric ceramic layer). agent twice the ratio of the components blended SiO ₂ in an amount such that (amount 0.11 wt% of SiO _2), after dispersion, the slurry was discharged in toluene / Ekinen, drying, heat treatment, Crushing was performed to produce a ceramic component (powder) to be added to the external electrode.

  Further, 22.6% by weight of the above ceramic component (powder) is added to 52.6% by weight of Ni powder having a particle size of 0.5 μm, and three rolls are added together with 24.8% by weight of varnish made of acrylic resin and terpineol. A conductive paste (Ni paste) was prepared by mixing and dispersing using

And after apply | coating this electrically conductive paste to the end surface which exposed the internal electrode of the unbaking laminated ceramic element, binder removal was performed by heat-processing at 250 degreeC in air | atmosphere for 5 hours.
Then, using a batch furnace capable of controlling the atmosphere of the multilayer ceramic element after debinding, the multilayer ceramic element and the external electrode were sintered by holding at 1250 ° C. in a reducing atmosphere for 2 hours, as shown in FIG. A multilayer ceramic capacitor having a simple structure was obtained.

And the characteristic was measured about the multilayer ceramic capacitor produced as mentioned above.
Incidentally, the design capacity characteristics here -55 ° C. to 125 ° C., 1V, the capacitance change rate at 1KHz to (ΔC / C ₂₀ ℃) were measured to examine the design capacity characteristics. Regarding the design capacity characteristics of this material system, those satisfying the capacity change rate (ΔC / C ₂₀ ° C) value or the JIS standard CH characteristics (0 ± 60 ppm) are evaluated as good (◯) and deviate. Were evaluated as having poor design capacity characteristics (×).
Table 5 shows the results.

  In the multilayer ceramic capacitor of Example 5, the composition of the main component of the dielectric ceramic layer forming material constituting the multilayer ceramic element (dielectric ceramic layer) and the composition of the ceramic component (powder) added to the external electrode are as described above. Although different from the case of Example 1, as shown in Table 5, it was confirmed that the same effect as that of Example 1 was obtained also in the case of the multilayer ceramic capacitor of Sample No. 20.

  Materials other than the dielectric ceramic layer forming material constituting the multilayer ceramic element (dielectric ceramic layer), the constituent material of the internal electrode, the metal material used for the external electrode, the ceramic component (powder) added to the external electrode, and the firing temperature A multilayer ceramic capacitor (sample No. 21 in Table 6) having the structure shown in FIG. 1 was produced under the same conditions as in Example 1 above.

In Example 6, 0.05Li ₂ O.0.30BaO was used as a sintering aid component with respect to the main component represented by (Ba _0.74 Sr _0.15 Ca _0.10 Mg _0.01 ) _1.01 (Ti _0.85 Zr _0.15 ) O _3. -After printing and laminating Cu internal electrodes on a ceramic green sheet using dielectric ceramic powder (dielectric material) containing 15% by weight of a glass component consisting of 0.30B ₂ O ₃ · 0.35SiO ₂ , By cutting and barrel polishing, an unfired multilayer ceramic element with the internal electrode exposed at the end face was produced. The dimensions of the multilayer ceramic element were 4.0 mm in length, 2.2 mm in width, and 2.2 mm in height.

Further, 100 g of a material having the same composition as the dielectric ceramic layer forming material constituting the multilayer ceramic element (dielectric ceramic layer) (average particle size is 0.3 μm and containing 15% by weight of the sintering aid component) On the other hand, the ratio of the sintering aid component contained in the ceramic component (powder) added to the external electrode is the sintering contained in the dielectric ceramic layer forming material constituting the multilayer ceramic element (dielectric ceramic layer). Li ₂ O is blended so that the ratio of the auxiliary component is 1.02 times (the amount of Li ₂ O added is 0.30% by weight), dispersed in toluene / echene, and then the slurry is discharged and dried. Then, heat treatment and pulverization were performed to prepare a ceramic component (powder) to be added to the external electrode.

  In addition, 22.6% by weight of the above ceramic component (powder) is added to 52.6% by weight of Cu powder having a particle size of 1.0 μm, and 3 rolls together with 24.8% by weight of varnish made of acrylic resin and terpineol. A conductive paste (Cu paste) was produced by mixing and dispersing using

And after apply | coating this electrically conductive paste to the end surface which exposed the internal electrode of the unbaking laminated ceramic element, binder removal was performed by heat-processing at 250 degreeC in air | atmosphere for 5 hours.
Then, the multilayer ceramic element after debinding is sintered at 950 ° C. in a reducing atmosphere using a batch furnace in which the atmosphere can be controlled, and the multilayer ceramic element and the external electrode are sintered. A multilayer ceramic capacitor having was obtained. And the characteristic was measured about the obtained multilayer ceramic capacitor. The results are shown in Table 6.

  In the multilayer ceramic capacitor of Example 6, the main component of the external electrode was changed to Cu as the internal electrode constituting the multilayer ceramic element was changed from Ni to Cu. In the case of the multilayer ceramic capacitor of sample number 21, it has been confirmed that the same effect as in Example 1 can be obtained.

  Materials other than the dielectric ceramic layer forming material constituting the multilayer ceramic element (dielectric ceramic layer), the constituent material of the internal electrode, the metal material used for the external electrode, the ceramic component (powder) added to the external electrode, and the firing temperature A multilayer ceramic capacitor (sample No. 22 in Table 7) was produced under the same conditions as in Example 1 above.

In Example 7, 0.05Li ₂ O.0.30BaO was used as a sintering aid component with respect to the main component represented by (Ba _0.74 Sr _0.15 Ca _0.10 Mg _0.01 ) _1.01 (Ti _0.85 Zr _0.15 ) O _3. After printing and laminating an Ag-Pd internal electrode on a ceramic green sheet made of dielectric ceramic powder (dielectric material) containing 15% by weight of a glass component made of 0.30B ₂ O ₃ .0.35SiO ₂ Then, by cutting and barrel polishing, an unfired multilayer ceramic element in which the internal electrodes were exposed on both end surfaces was produced. The size of this multilayer ceramic element was 4.0 mm in length, 2.2 mm in width, and 2.2 mm in height.

Further, 100 g of a dielectric material having the same composition as the dielectric ceramic layer forming material constituting the multilayer ceramic element (dielectric ceramic layer) (average particle size is 0.3 μm and containing 15% by weight of the sintering aid component) On the other hand, the ratio of the sintering aid component contained in the ceramic component (powder) added to the external electrode is a firing ratio contained in the dielectric ceramic layer forming material constituting the multilayer ceramic element (dielectric ceramic layer). 1.02 times the ratio of the aid component (Li ₂ O amount 0.30 wt%) were blended Li ₂ O so that, after dispersion, the slurry was discharged in toluene / Ekinen, The ceramic component (powder) added to an external electrode was produced by drying, heat treatment, and crushing.

  In addition, 22.6% by weight of the above ceramic component (powder) is added to 52.6% by weight of Ag powder having a particle size of 1.0 μm, and three varnishes containing 24.8% by weight of varnish made of acrylic resin and terpineol A conductive paste (Ag paste) was prepared by mixing and dispersing using a roll.

And after apply | coating this electrically conductive paste to the end surface which exposed the internal electrode of the unbaked multilayer ceramic element, the binder removal was performed by heat-processing at 250 degreeC in air | atmosphere for 5 hours.
Then, the multilayer ceramic element after debinding was fired at 950 ° C. in an air atmosphere to sinter the multilayer ceramic element and the external electrode, and a multilayer ceramic capacitor having a structure as shown in FIG. 1 was produced. .

  The characteristics of the multilayer ceramic capacitor obtained as described above were measured. The results are shown in Table 7 (Sample No. 22).

  As shown in Table 7, even when the main electrode of the external electrode is changed to Ag as the internal electrode constituting the multilayer ceramic element is changed from Ni to Ag, the same effect as in the case of Example 1 described above is obtained. It was confirmed that

  In each of the above embodiments, Ni, Cu, and Ag are used as the main component of the external electrode. However, in the present invention, there are no particular restrictions on the type of conductive component that constitutes the external electrode. It is also possible to use a metal powder other than Ag, an alloy containing at least one of Ni, Cu, and Ag, or an alloy containing Pd in Ag.

  In each of the above-described embodiments, the multilayer ceramic capacitor has been described as an example. However, the present invention is not limited to the multilayer ceramic capacitor, but can be widely applied to various multilayer ceramic electronic components such as multilayer ceramic LC composite components and multilayer ceramic substrates. Is possible.

  The present invention is not limited to the above embodiments in other points, and various applications and modifications can be made within the scope of the invention.

According to the present invention, it is possible to efficiently form a dense external electrode having high adhesion strength with the multilayer ceramic element, and it is possible to provide a highly reliable multilayer ceramic electronic component.
Therefore, the present invention can be widely applied to monolithic ceramic electronic components such as monolithic ceramic capacitors, monolithic ceramic LC composite parts, multilayer ceramic substrates, and manufacturing processes thereof.

1 is a cross-sectional view schematically illustrating a multilayer ceramic electronic component (multilayer ceramic capacitor) according to an embodiment of the present invention. (a), (b) is a figure explaining the manufacturing method of the multilayer ceramic electronic component (multilayer ceramic capacitor) concerning one Example of this invention. It is a figure which shows the conventional multilayer ceramic electronic component (multilayer ceramic capacitor).

Explanation of symbols

1 Multilayer Ceramic Element 1a Unfired Multilayer Ceramic Element
2a, 2b Internal electrode
3 Ceramic layer 4a, 4b End face of multilayer ceramic element 5a, 5b External electrode 6a, 6b Ni plating layer 7a, 7b Sn plating layer 10 Multilayer ceramic capacitor 15a, 15b Conductive paste (Ni paste)

Claims (8)

A method for producing a multilayer ceramic electronic component having a structure comprising a multilayer ceramic element having a structure in which a dielectric ceramic layer and internal electrodes are laminated, and an external electrode formed on the surface of the multilayer ceramic element,
(a) A material containing a conductive component and a ceramic component as the external electrode forming material for forming the external electrode, wherein the ceramic component contains a ceramic material powder and a sintering aid [A]. Use
(b) As a dielectric ceramic layer forming material for forming the dielectric ceramic layer, a material containing a dielectric ceramic powder and a sintering aid [B] is used.
(c) content C _B (weight of content C _A (wt%), sintering aid of the dielectric ceramic layer forming material [B] of the sintering aid in ceramic component [A] %): C _A / C _{B is set} to a ratio that satisfies the requirement of the formula: 1 <C _A / C _B ≦ 3,
A step of simultaneously and integrally firing unfired multilayer ceramic elements formed using the dielectric ceramic layer forming material, the external electrode forming material, and the internal electrode forming material. A method for producing a multilayer ceramic electronic component. The sintering aid [A] and the sintering aid [B] is, according to claim 1, wherein the at least one selected from the group consisting of _{SiO 2, B 2 O 3,} Li 2 O Manufacturing method for multilayer ceramic electronic parts.   The method for manufacturing a multilayer ceramic electronic component according to claim 1 or 2, wherein the conductive component constituting the external electrode is at least one selected from the group consisting of Ni, Cu, and Ag.   The ratio of the ceramic component in the external electrode forming material for forming the external electrode to the total amount of the conductive component and the ceramic component is in the range of 10 to 50% by weight. The manufacturing method of the multilayer ceramic electronic component in any one. A multilayer ceramic element having a structure in which a dielectric ceramic layer and an internal electrode are laminated; and an external electrode formed on a surface of the multilayer ceramic element, the dielectric ceramic layer forming material, A multilayer ceramic electronic component manufactured through a step of simultaneously and integrally firing unfired multilayer ceramic elements formed using the external electrode forming material and the internal electrode forming material,
(a) The external electrode contains a conductive component and a ceramic component, and the ceramic component contains a ceramic material and a sintering aid [A],
(b) The dielectric ceramic layer contains a dielectric ceramic material and a sintering aid [B],
(c) content C _B (weight of content C _A (% by weight), sintering aid of the dielectric ceramic layer forming material [B] of the sintering aid in ceramic component [A] %): C _A / C _B satisfies the requirement of the formula: 1 <C _A / C _B ≦ 3. The sintering aid [A] and the sintering aid [B] _{is, SiO 2, B 2 O 3} , it claim 5, wherein at least one selected from the group consisting of Li ₂ O Multilayer ceramic electronic components.   The multilayer ceramic electronic component according to claim 5 or 6, wherein the conductive component constituting the external electrode is at least one selected from the group consisting of Ni, Cu, and Ag.   The ratio of the ceramic component in the external electrode forming material for forming the external electrode to the total amount of the conductive component and the ceramic component is in the range of 10 to 50% by weight. The multilayer ceramic electronic component according to any one of the above.

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