JP2021072158A - Conductive paste and laminated electronic component - Google Patents

Abstract

To provide a conductive paste that is baked to give a primer electrode layer having high humidity resistance.SOLUTION: A conductive paste 1 has a conductive powder 2 having at least one element selected from Cu and Ni, glass powder 3, and organic material 4. The glass powder 3 has a borosilicate glass composition. If the amounts of elements contained in the borosilicate glass composition are expressed in mol%, when the amount of four-coordinated B is defined as CB4 and the amount of three-coordinated B is defined as CB3, the abundance ratio RB4 of the four-coordinated B expressed by CB4/(CB4+CB3) satisfies 0.35≤RB4≤0.80.SELECTED DRAWING: Figure 1

Description

This disclosure relates to a conductive paste containing glass powder and a laminated electronic component having an external electrode formed using the conductive paste.

The external electrode of a laminated electronic component such as a laminated ceramic capacitor generally includes a base electrode layer formed on the surface of the laminated body and a plating layer applied on the base electrode layer. The base electrode layer is often a sintered body layer formed by baking a conductive paste containing a conductive powder such as Cu and Ni, a glass powder, and an organic material. Here, since the thickness of the plating layer is extremely thin, the thickness of the external electrode is affected by the thickness of the base electrode layer.

For example, as one means for promoting the miniaturization and large capacity of the multilayer ceramic capacitor, it is possible to make the thickness of the external electrode as thin as possible and increase the volume of the laminate expressing the capacitance. For that purpose, it is necessary to reduce the thickness of the base electrode layer. On the other hand, if the base electrode layer is made thin, there is a risk that moisture easily infiltrates from the outside. The glass powder in the conductive paste is added in order to improve the sinterability of the conductive powder and suppress the infiltration of moisture from the outside, that is, to obtain a base electrode layer having high moisture resistance.

As a component of the glass powder, a borosilicate glass composition containing oxides of B and Si as a network-forming oxide and an oxide of an alkali metal element and an oxide of an alkaline earth metal element as a network-modifying oxide is used. Is often done. Oxides of alkaline earth metal elements are added to suppress the reaction between the above glass composition and the laminate during baking of the conductive paste. As an example of the conductive paste containing the glass powder using the borosilicate glass composition as described above, the conductive paste described in International Publication No. 2017/057246 (Patent Document 1) can be mentioned.

International Publication No. 2017/05/7246

By the way, the borosilicate glass composition contains 3-coordinated B and 4-coordinated B. B in the borosilicate glass composition containing an alkaline earth metal element facilitates tricoordination. If the tri-coordinated B increases, the moisture resistance of the base electrode layer formed by baking the conductive paste may decrease. However, Patent Document 1 does not mention the ratio of the tri-coordinated B to the 4-coordinated B in the borosilicate glass composition and the relationship between the ratio and the moisture resistance.

The purpose of this disclosure is to focus on the coordination number of B, and to provide a conductive paste capable of obtaining a base electrode layer having high moisture resistance by baking, and an external electrode including a base electrode layer formed by using the conductive paste. It is to provide a laminated electronic component.

The conductive paste according to this disclosure includes a conductive powder containing at least one element selected from Cu and Ni, a glass powder, and an organic material. The glass powder contains a borosilicate glass composition. When the amount of the element contained in the borosilicate glass composition is expressed in mol%, when the amount of 4-coordinated B is C _B4 and the amount of 3-coordinated B is C _B3 , C _{B4 The abundance ratio R B4} of the four-coordinated B represented by / (C _B4 + C _B3 ) satisfies 0.35 ≤ R _B4 ≤ 0.80.

The laminated electronic component according to the present disclosure is formed in a laminated body including a plurality of laminated dielectric layers and a plurality of internal electrode layers at different positions on the outer surface of the laminated body, and is formed on the internal electrode layer. It has a plurality of external electrodes that are electrically connected. The external electrode includes a base electrode layer having a conductive region containing at least one element selected from Cu and Ni and a glass region containing a borosilicate glass composition. When the amount of the element contained in the borosilicate glass composition is expressed in mol%, when the amount of 4-coordinated B is C _B4 and the amount of 3-coordinated B is C _B3 , C _{B4 The abundance ratio R B4} of the four-coordinated B represented by / (C _B4 + C _B3 ) satisfies 0.35 ≤ R _B4 ≤ 0.80.

The conductive paste according to this disclosure can obtain a base electrode layer having high moisture resistance. Further, the laminated electronic component according to the present disclosure may include an external electrode including a base electrode layer having high moisture resistance.

It is a schematic diagram of the conductive paste 1 which is the embodiment of the conductive paste which concerns on this disclosure. This is an actual measurement example of an NMR spectrum focusing on B of a borosilicate glass composition. This is the result of signal separation by simulating the NMR spectrum focusing on B of the borosilicate glass composition. It is sectional drawing of the multilayer ceramic capacitor 100 which is the embodiment of the laminated electronic component which concerns on this disclosure. It is sectional drawing for _{demonstrating the microstructure of the 1st base electrode layer 14a 1} of the 1st external electrode 14a of a multilayer ceramic capacitor 100. It is a scanning transmission X-ray microscope (hereinafter, abbreviated as STXM) spectrum obtained from a reference material in which C _{B4 in B is known.} 6 is a graph showing the relationship between the A / B ratio of the STXM spectrum obtained from a reference material in which _{C B4 in B is known and C B4.}

The features of this disclosure will be described with reference to the drawings. In the embodiment of the laminated electronic component shown below, the same or common parts may be designated by the same reference numerals in the drawings, and the description thereof may not be repeated.

-Embodiment of Conductive Paste-
The conductive paste 1 showing the embodiment of the conductive paste according to this disclosure will be described with reference to FIGS. 1 to 3.

<Construction of conductive paste>
FIG. 1 is a schematic view of the conductive paste 1. The conductive paste 1 includes a conductive powder 2, a glass powder 3, and an organic material 4.

The conductive powder 2 contains at least one element selected from Cu and Ni. That is, the conductive powder 2 may contain not only a simple substance of Cu or Ni metal but also a Cu alloy or Ni alloy.

Further, at least a part of the surface of the conductive powder 2 may be coated with a metal layer containing at least one element selected from Ag, Sn and Al. The above metal elements have a lower melting point than Cu and Ni. Therefore, the conductive powder 2 having the above structure can lower the sintering temperature.

Further, at least a part of the surface of the conductive powder 2 may be coated with an organic substance layer. In this case, for example, the presence of an organic layer can provide effects such as steric hindrance repulsion or electrostatic repulsion. As a result, even if the conductive powder 2 is fine particles, the aggregation of the conductive powder 2 in the conductive paste 1 can be suppressed.

The average particle size of the conductive powder 2 is preferably 1 μm or less. The average particle size of the conductive powder 2 is the median diameter of the equivalent circle-equivalent diameter obtained from the image analysis of the scanning electron microscope (hereinafter sometimes abbreviated as SEM) observation image of the conductive powder 2. And said. _{The median diameter of the equivalent circle-equivalent diameter is the particle size (D 50} ) at which the integrated% is 50% in the distribution curve of the integrated% with respect to the particle size. In this case, the conductive powder 2 can lower the sintering temperature.

The glass powder 3 is the glass powder according to this disclosure. The characteristics of the glass powder 3 will be described later. In FIG. 1, the conductive powder 2 and the glass powder 3 are schematically drawn in a spherical shape, but the shape of each powder is not limited to this. For example, the conductive powder 2 may contain a flat conductive powder. The glass powder 3 may also contain an irregularly shaped glass powder.

The organic material 4 contains a binder component including a resin and an organic solvent, and an additive containing a dispersant, a rheology control agent, and the like. These components can be appropriately selected from the materials usually used as the organic material of the conductive paste.

The glass powder 3 contains a borosilicate glass composition. The borosilicate-based glass composition is a glass composition containing B oxide and Si oxide as network-forming oxides, and containing alkali metal element oxides, alkaline earth metal element oxides and the like as modified oxides. The modified oxide may contain oxides other than the above, such as transition metal element oxides, Zn oxides, Al oxides and Bi oxides.

When the amount of the element contained in the borosilicate glass composition is expressed in mol%, when the amount of 4-coordinated B is C _B4 and the amount of 3-coordinated B is C _B3 , C _{B4 The abundance ratio R B4} of the four-coordinated B represented by / (C _B4 + C _B3 ) satisfies 0.35 ≤ R _B4 ≤ 0.80.

Measurement of the amount C _B3 of the amount C _B4 and 3 coordination tetracoordinate B contained in B borosilicate glass composition B, nuclear magnetic resonance (Nuclear Magnetic Resonance: hereinafter, abbreviated as NMR Is done by the device.

The measurement and analysis of the NMR spectrum will be further described with reference to FIGS. 2 and 3. FIG. 2 is an actual measurement example of an NMR spectrum focusing on B of the borosilicate glass composition. The measurement conditions will be described later. FIG. 3 shows the results of signal separation by simulation of the NMR spectrum focusing on B of the borosilicate glass composition.

Assuming that B in the borosilicate glass composition contains 4-coordinated B and 3-coordinated _B , the ratio of _{the amount C B4} of 4-coordinated B to the amount C B3 of 3-coordinated B is changed. By doing so, the simulation spectrum of NMR at each ratio was calculated (solid line). Then, by fitting the spectrum shown in FIG. 2 with the actual measurement example and obtaining the ratio that maximizes the matching rate, the signal (dashed line) derived from the 4-coordinated B and the 3-coordinated B (dashed line) are obtained. Separation from the signal derived from (dotted line) was performed.

Here, the fitting was performed in the range of -40 ppm to 50 ppm of the chemical shift. The ratio of the 4-coordinated B quantity C _B4 to the 3-coordinated B quantity C _B3 was calculated from the area strength of each signal minus the background signal.

For example, the concordance rate between the actual measurement example of the NMR spectrum shown in FIG. 2 and the simulation result (solid line) derived from B shown in FIG. 3 is 97% or more when the chemical shift is in the range of -40 ppm to 50 ppm. there were. The amount of 4-coordinated B C _{B4 at} that time was 38 mol%, and the amount of 3-coordinated B C _B3 was 62 mol%.

When the abundance ratio R _B4 of 4-coordinated B is 0.35 or more, the stability of B in the borosilicate glass composition contained in the glass powder 3 is improved. In other words, the crosslinked structure of B and O in the glass network structure is stable. Therefore, the elution of B in the borosilicate glass composition due to the moisture contained in the environment is suppressed.

_{The higher the abundance ratio R B4} of 4-coordinated B is, the greater the above effect is, but when R _B4 exceeds 0.80, the stability of the glass composition is lowered. Therefore, the abundance ratio R _B4 of the four-coordinated B is substantially 0.35 ≦ R _B4 ≦ 0.80.

Since the conductive paste 1 according to the present disclosure includes the glass powder 3 having the above-mentioned characteristics, high moisture resistance can be obtained in the base electrode obtained by baking the conductive paste 1.

Borosilicate glass composition contained in the glass powder 3 includes a first element A and second element AE, the amount of the first element A and C _A, the amount of the second element AE C _AE when a, it is preferable that C _a + C _AE satisfies _{11.7 ≦ C a + C AE ≦} 53.4. Here, the first element A is at least one element selected from Li, Na and K, and the second element AE is at least one element selected from Ba, Sr and Ca. Is. In this case, the abundance ratio R _B4 of the four-coordinated B can be easily adjusted.

The borosilicate glass composition contained in the glass powder 3 _{preferably satisfies the above C AE} of 9.4 ≤ C _AE ≤ 47.1. _{In this case, in addition to being able to easily adjust the abundance ratio R B4} of 4-coordinated B, it is possible to improve the deflection strength of the multilayer ceramic capacitor provided with the base electrode obtained by baking the conductive paste 1. it can.

-Embodiment of laminated electronic components-
The multilayer ceramic capacitor 100 showing an embodiment of the laminated electronic component according to this disclosure will be described with reference to FIGS. 4 and 5.

FIG. 4 is a cross-sectional view of the multilayer ceramic capacitor 100. The multilayer ceramic capacitor 100 includes a laminate 10. The laminated body 10 includes a plurality of laminated dielectric layers 11 and a plurality of internal electrode layers 12. The plurality of dielectric layers 11 have an outer layer portion and an inner layer portion. The outer layer portion is between the first main surface and the inner electrode layer 12 closest to the first main surface of the laminate 10, and the inner electrode layer 12 closest to the second main surface and the second main surface. It is placed between. The inner layer portion is arranged in the region sandwiched between the two outer layer portions.

The plurality of internal electrode layers 12 have a first internal electrode layer 12a and a second internal electrode layer 12b. The laminated body 10 has a first main surface and a second main surface facing the stacking direction, a first side surface and a second side surface facing the width direction orthogonal to the stacking direction, and the stacking direction and the width direction. It has a first end face 13a and a second end face 13b that face each other in the orthogonal length directions.

The dielectric layer 11 has a _{plurality of crystal grains containing, for example, a BaTiO 3-} based perovskite-type compound. Examples of the above-mentioned dielectric material include ^{those in which a part of Ba 2+ in} _{the crystal lattice of a BaTiO 3-} based perovskite-type compound is replaced by ^{Re 3+,} which is an ion of a rare earth element. In addition, as the BaTIO ₃ type perovskite type compound, BaTIO ₃ and at least one of Ba ²⁺ and Ti ⁴⁺ _{of BaTIO 3} are substituted with other ions such as ^{Ca 2+} and Zr ^4+. Can be mentioned.

The first internal electrode layer 12a has a counter electrode portion facing the second internal electrode layer 12b via the dielectric layer 11 and a lead-out from the counter electrode portion to the first end surface 13a of the laminated body 10. It is equipped with an electrode unit. The second internal electrode layer 12b has a counter electrode portion facing the first internal electrode layer 12a via the dielectric layer 11 and a lead-out from the counter electrode portion to the second end surface 13b of the laminated body 10. It is equipped with an electrode unit.

One capacitor is formed by the first internal electrode layer 12a and the second internal electrode layer 12b facing each other via the dielectric layer 11. It can be said that the multilayer ceramic capacitor 100 has a plurality of capacitors connected in parallel via a first external electrode 14a and a second external electrode 14b, which will be described later.

As the conductive material constituting the internal electrode layer 12, at least one metal selected from Ni, Cu, Ag, Pd and the like, or an alloy containing the metal can be used. The internal electrode layer 12 may further contain dielectric particles called co-materials (not shown) as described later. The common material is added to the paste for the internal electrode layer used for forming the internal electrode layer 12, and is discharged to the dielectric layer 11 side when the laminate 10 is fired, but a part of the common material is discharged to the dielectric layer 11 side. It may remain in layer 12. The co-material is added in order to bring the sintering shrinkage characteristic of the internal electrode layer 12 closer to the sintering shrinkage characteristic of the dielectric layer 11 at the time of firing the laminated body 10.

The multilayer ceramic capacitor 100 further includes a first external electrode 14a and a second external electrode 14b. The first external electrode 14a is formed on the first end surface 13a of the laminate 10 so as to be electrically connected to the first internal electrode layer 12a, and the first end surface 13a to the first main surface and the first surface are formed. It extends to two main surfaces and a first side surface and a second side surface. The second external electrode 14b is formed on the second end surface 13b of the laminate 10 so as to be electrically connected to the second internal electrode layer 12b, and the second end surface 13b to the first main surface and the first surface are formed. It extends to the main surface of 2 and the first side surface and the second side surface.

The first external electrode 14a has a first base electrode layer 14a ₁ and a first plating layer 14a ₂ arranged on the first base electrode layer 14a ₁ . The first base electrode layer 14a ₁ is a sintered body having _{a conductive region 15a 1} containing at least one element selected from Cu and Ni _{and a glass region 16a 1} containing a borosilicate glass composition. It has a layer (described later). The first base electrode layer 14a ₁ may be formed by baking the conductive paste 1 according to this disclosure.

Similarly, the second external electrode 14b has a second base electrode layer 14b ₁ and a second plating layer 14b ₂ arranged on the second base electrode layer 14b ₁ . The second base electrode layer 14b ₁ has a sintered body layer having a conductive region containing at least one element selected from Cu and Ni and a glass region containing a borosilicate glass composition ( The microstructure of the second base electrode layer 14b ₁ is not shown). The second base electrode layer 14b ₁ may also be formed by baking the conductive paste 1 according to this disclosure.

FIG. 5 is a cross-sectional view for explaining the fine structure of the _{first base electrode layer 14a 1.} Since the second base electrode layer 14b _{1 has the same structure as the first} base electrode layer 14a 1, the following description will be omitted.

The sintered body layer included in the first base electrode layer 14a _{1 includes a conductive region 15a 1} and a glass region 16a ₁ as described above. When the first base electrode layer 14a ₁ is formed by baking the conductive paste 1 according to the present disclosure, the conductive region 15a ₁ is a metal sintered body obtained by sintering the conductive powder 2 included in the conductive paste 1. Includes. Similarly, the glass region 16a ₁ contains a glass component derived from the glass powder 3, that is, a borosilicate glass composition. The sintered body layer may be formed of a plurality of layers with different components.

As the metal constituting the first plating layer 14a ₂ arranged on the first base electrode layer 14a ₁ , at least one selected from Ni, Cu, Ag, Au, Sn and the like, or an alloy containing the metal is used. be able to. The plating layer may be formed of a plurality of layers with different components. Two layers, a Ni plating layer and a Sn plating layer, are preferable.

The Ni plating layer is arranged on the base electrode layer, and can prevent the base electrode layer from being eroded by the solder when mounting the laminated electronic component. The Sn plating layer is arranged on the Ni plating layer. Since the Sn plating layer has good wettability with the solder containing Sn, the mountability can be improved when mounting the laminated electronic component. In addition, these plating layers are not indispensable.

When the amount of the element contained in the borosilicate glass composition in the glass region 16a ₁ is expressed in mol%, the amount of 4-coordinated B is defined as C _B4, and the amount of tri-coordinated B is defined as C _B3 . Then, _{the abundance ratio R B4} of the four-coordinated B represented by _{C B4} / (C _B4 + C _B3 ) satisfies 0.35 ≤ R _B4 ≤ 0.80. As described above, the glass region in the second base electrode layer 14b ₁ has the same characteristics.

_{The amount C B4} of 4-coordinated B and the amount C _B3 of tri-coordinated B contained in B of the borosilicate glass composition are measured by a scanning transmission X-ray microscope (STXM). The STXM is a device that detects a transmitted signal when a finely focused X-ray beam is relatively scanned on a sample by moving a sliced sample. The transmitted signal usually refers to the transmitted X-ray intensity. Here, the absorption intensity can be easily obtained by taking the ratio of the transmitted X-ray intensity and the incident X-ray intensity. That is, an STXM spectrum is obtained by obtaining a plurality of two-dimensional absorption images in which the intensity of each energy is measured based on the measurement energy range and the energy step condition, and superimposing them.

For example, the measurement energy range from the measurement start energy E _A (eV) to the measurement end energy E _B (eV) is divided into C energy steps according to the set energy step width (eV). Then, by measuring the absorption intensity at each energy step, C two-dimensional absorption images can be obtained. The energy step width may be changed within the measured energy range. The STXM spectrum is obtained by superimposing the obtained C absorption images. By analyzing this STXM spectrum, it is possible to obtain information on the chemical bond state of the sample.

The measurement and analysis of the STXM spectrum will be further described with reference to FIGS. 6 and 7. FIG. 6 is an STXM spectrum obtained from a reference material in which _{C B4} in B in a borosilicate glass composition is known. The measurement conditions will be described later.

In STXM, since synchrotron radiation is used as the light source (X-ray source), the photon energy (wavelength) of the incident X-ray can be easily changed. When the photon energy of incident X-rays is changed in the vicinity of the ionization energy of the core electrons of the elements constituting the sample, the absorption of X-rays increases above a certain threshold. This threshold is the so-called absorption edge. Further, when the absorption intensity of X-rays is examined in detail in the vicinity of the absorption edge, a structure peculiar to the absorption spectrum appears depending on the chemical bond state of the element of interest. This unique structure is referred to as an X-ray absorption fine structure (hereinafter, may be abbreviated as XAFS).

In this disclosure, the spectrum in which the XAFS obtained from each sample appears is referred to as the STXM spectrum. STXM is used to elucidate the chemical state in a minute part by utilizing the fact that this STXM spectrum changes according to the chemical bond state of the element of interest.

It can be seen that the STXM spectrum at the K-edge of B ^{contains peaks due to π *} bonds and σ ^{* bonds of the BO coordination structure by performing peak separation.} The STXM spectrum of FIG. 6 includes a spire-shaped π ^{* peak described as Energy A near 194 eV and a broad σ *} peak described as Energy B near 198 eV and Energy C near 203 eV. The STXM spectrum in FIG. 6 includes other broad peaks, but the following analysis is derived from B in which ^{the π *} peak has three coordinations (sp ² structure: BO ₃ ^{), and the σ *} peak. Was derived from B in 4-coordination (sp ³ structure: BO _4).

Here, the three kinds of STXM spectrum shown in FIG. 6, Energy peak intensity of A, between the A / B ratio and C _B4 is the ratio to the peak intensity of the Energy B, primary correlation It turned out that there is.

FIG. 7 is a graph showing the relationship between _{the A / B ratio and C B4 of} the STXM spectrum obtained from three types of reference materials in which _{C B4 in B is known.} That is, by using this graph as a calibration curve, the values of _{C B4} and C _B3 can be calculated from the A / B ratio in the STXM spectrum of the borosilicate glass composition. Then, _{the abundance ratio R B4} of the four-coordinated B represented by _{C B4} / (C _B4 + C _B3 ) can be calculated.

When the abundance ratio R _B4 of 4-coordinated B is 0.35 or more, the stability of B in the borosilicate glass composition in the glass region is improved. In other words, the crosslinked structure of B and O in the glass network structure is stable. Therefore, the elution of B in the borosilicate glass composition due to the moisture contained in the environment is suppressed.

_{The higher the abundance ratio R B4} of 4-coordinated B is, the greater the above effect is, but when R _B4 exceeds 0.80, the stability of the glass composition is lowered. Therefore, the abundance ratio R _B4 of the four-coordinated B is substantially 0.35 ≦ R _B4 ≦ 0.80.

The multilayer ceramic capacitor 100 according to the present disclosure can include an external electrode including a base electrode layer having high moisture resistance by having a glass region having the above-mentioned characteristics.

Borosilicate glass composition contained in the glass region comprises a first element A and second element AE, the amount of the first element A and C _A, the amount of the second element AE and C _AE when, it is preferable that C _a + C _AE satisfies _{11.7 ≦ C a + C AE ≦} 53.4. Here, the first element A is at least one element selected from Li, Na and K, and the second element AE is at least one element selected from Ba, Sr and Ca. Is. In this case, the abundance ratio R _B4 of the four-coordinated B can be easily adjusted.

In the borosilicate glass composition contained in the glass region, it is preferable that _{the above C AE} satisfies 9.4 ≤ C _{AE ≤ 47.1. In this case, in addition to being able to easily adjust the abundance ratio R B4} of 4-coordinated B, it is possible to improve the deflection strength of the multilayer ceramic capacitor provided with the base electrode obtained by baking the conductive paste 1. it can.

-Experimental example-
The conductive paste and the laminated electronic component according to this disclosure will be described more specifically based on the following experimental examples. These experimental examples are also for providing a basis for defining the conditions of the conductive paste and the laminated electronic component according to this disclosure, or more preferable conditions. In the experimental example, the glass powders of sample numbers 1 to 17 were prepared, and the abundance ratio of 4-coordinated B in B in the borosilicate glass composition contained in the glass powder was evaluated by NMR.

Further, a conductive paste was prepared using the glass powders of sample numbers 1 to 17, Cu powder having an average particle size of 0.5 μm confirmed by image analysis of SEM observation images, and an organic material, and these were used. A multilayer ceramic capacitor as shown in FIG. 4 in which the base electrode layer of the external electrode was formed was produced. The dielectric layer in the laminated body of the multilayer ceramic capacitor is _{formed of a dielectric material containing a BaTiO 3-} based perovskite type compound, and the internal electrode layer is formed of Ni.

Using these multilayer ceramic capacitors, the abundance ratio of 4-coordinated B in B in the borosilicate glass composition contained in the glass region of the base electrode layer was evaluated by STXM. Further, the moisture resistance of the multilayer ceramic capacitor produced as described above was evaluated by a high temperature and high humidity bias test (Pressure Cooker Bias Test: hereinafter abbreviated as PCBT). In addition, the deflection strength of the multilayer ceramic capacitor produced as described above was evaluated based on the deflection test method based on the JIS standard.

The NMR evaluation of the abundance ratio of 4-coordinated B in B in the borosilicate glass composition contained in the glass powders of Sample Nos. 1 to 20 was carried out under the conditions shown in Table 1.

The abundance ratio of 4-coordinated B in B in the borosilicate glass composition contained in the glass region of the base electrode layer formed by baking the conductive paste containing the glass powders of Sample Nos. 1 to 20. The evaluation by STXM was performed under the conditions shown in Table 2.

The moisture resistance of the multilayer ceramic capacitor having the base electrode layer formed by baking the conductive paste containing the glass powders of Sample Nos. 1 to 20 was evaluated under the conditions shown in Table 3.

The flexural strength of the multilayer ceramic capacitor having the base electrode layer formed by baking the conductive paste containing the glass powders of Sample Nos. 1 to 20 was evaluated under the conditions shown in Table 4.

Evaluation result by NMR of the abundance ratio of 4-coordinated B in the glass powder, evaluation result by STXM of the abundance ratio of 4-coordinated B in the glass region of the base electrode layer, and evaluation result of the moisture resistance of the multilayer ceramic capacitor. Are collectively shown in Table 5. Sample numbers marked with * in Table 5 are samples that do not meet the conditions that specify the conductive paste according to this disclosure.

In addition, the evaluation result of the deflection strength of the multilayer ceramic capacitor excluding the sample judged to be defective in the evaluation result of the moisture resistance is the evaluation of the abundance ratio of 4-coordinated B in the glass powder and the glass region of the base electrode layer. The results are summarized in Table 6.

In addition, the evaluation result by NMR of the abundance ratio of 4-coordinated B in the glass powder in Tables 5 and 6 and the evaluation result by STXM of the abundance ratio of 4-coordinated B in the glass region of the base electrode layer are 3 It is the average value of the measurement results obtained from each of the two samples. That is, the characteristic numerical range of the 4-coordination B in this disclosure is defined from the average value of a plurality of measurement results. In other words, whether or not it is within the numerical range in this disclosure is determined by comparing the average value of a plurality of measurement results obtained from the comparison object with the numerical range in this disclosure.

The evaluation result of the abundance ratio of 4-coordinated B in the glass powder by NMR and the 4-coordinated B in the glass region of the base electrode layer formed by baking the conductive paste using the glass powder. It was confirmed that the abundance ratio was in agreement with the evaluation result by NMR. That is, when the conductive paste is baked, the amount of B and the chemical bond state in the borosilicate glass composition are essentially unchanged. In other words, the abundance ratio of 4-coordinated B in the glass region of the base electrode layer in the state of the multilayer ceramic capacitor can be estimated from the abundance ratio of 4-coordinated B in the glass powder provided by the conductive paste. it can.

As shown in Table 5, it was confirmed that the moisture resistance was good in each sample of the multilayer ceramic capacitor satisfying the conditions for defining the conductive paste according to this disclosure. Further, as shown in Table 6, it was confirmed that the deflection strength was also good in each of the above samples.

The embodiments disclosed in this specification are exemplary, and the invention according to this disclosure is not limited to the above-described embodiments. That is, the scope of the invention according to this disclosure is indicated by the scope of claims, and is intended to include all modifications within the meaning and scope equivalent to the scope of claims. Moreover, various applications and modifications can be added within the above range.

For example, various applications and modifications can be applied within the scope of the present invention with respect to the number of layers of the dielectric layer and the internal electrode layer constituting the laminated body, the material of the dielectric layer and the internal electrode layer, and the like. Further, although a laminated ceramic capacitor has been exemplified as a laminated electronic component, the invention according to this disclosure is not limited to this, and can be applied to a capacitor element formed inside a multilayer substrate and the like.

Moreover, the number and location of external electrodes is not limited to the embodiments disclosed herein. That is, a plurality of external electrodes may be formed at different positions on the outer surface of the laminated body and may be electrically connected to the internal electrode layer.

1 Conductive paste 2 Conductive powder 3 Glass powder 4 Organic material 100 Laminated ceramic capacitor 10 Laminated body 11 Dielectric layer 12 Internal electrode layer 13a First end face 13b Second end face 14a First external electrode 14a ₁ First Base electrode layer 14a ₂ First plating layer 14b Second external electrode 14b ₁ Second base electrode layer 14b ₂ Second plating layer 15a ₁ Conductive region 16a ₁ Glass region A First element AE Second element

Claims (9)

It comprises a conductive powder containing at least one element selected from Cu and Ni, a glass powder, and an organic material.
The glass powder contains a borosilicate glass composition and contains.
When the amount of the element contained in the borosilicate glass composition is expressed in mol%, when the amount of 4-coordinated B is C _B4 and the amount of 3-coordinated B is C _B3 , C _B4 / A conductive paste in which _{the abundance ratio R B4} of 4-coordinated B represented by (C _B4 + C _B3 ) satisfies 0.35 ≤ R _{B4 ≤ 0.80.} The borosilicate glass composition contains at least one first element A selected from Li, Na and K, and at least one second element AE selected from Ba, Sr and Ca. Including
The amount of the first element A and C _A, when the amount of the second element AE was C _AE, C _A + C _AE satisfies _{11.7 ≦ C A + C AE ≦} 53.4, claim The conductive paste according to 1. The conductive paste according to claim 2, wherein the C _AE satisfies 9.4 ≤ C _{AE ≤ 47.1.} The method according to any one of claims 1 to 3, wherein at least a part of the surface of the conductive powder is coated with a metal layer containing at least one element selected from Ag, Sn and Al. Conductive paste. The conductive paste according to any one of claims 1 to 4, wherein at least a part of the surface of the conductive powder is coated with an organic substance layer. The conductive paste according to any one of claims 1 to 5, wherein the conductive powder has an average particle size of 1 μm or less. A plurality of laminated bodies including a plurality of laminated dielectric layers and a plurality of internal electrode layers, and a plurality of laminated bodies formed at different positions on the outer surface of the laminated body and electrically connected to the internal electrode layers. With external electrodes,
The external electrode includes a base electrode layer having a conductive region containing at least one element selected from Cu and Ni and a glass region containing a borosilicate glass composition.
When the amount of elements contained in the borosilicate glass composition is expressed in mol%, when the amount of 4-coordinated B is C _B4 and the amount of 3-coordinated B is C _B3 , C _B4 / A laminated electronic component in which _{the abundance ratio R B4} of 4-coordinated B represented by (C _B4 + C _B3 ) satisfies 0.35 ≤ R _{B4 ≤ 0.80.} The borosilicate glass composition contains at least one first element A selected from Li, Na and K, and at least one second element AE selected from Ba, Sr and Ca. Including
The amount of the first element A and C _A, when the amount of the second element AE was C _AE, C _A + C _AE satisfies _{11.7 ≦ C A + C AE ≦} 53.4, claim 7. The laminated electronic component according to 7. The laminated electronic component according to claim 8, wherein the C _AE satisfies 9.4 ≤ C _{AE ≤ 47.1.}

Images