JP7369008B2 - Conductive paste and laminated electronic components - Google Patents

Description

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

External electrodes of multilayer electronic components such as multilayer ceramic capacitors generally include a base electrode layer formed on the surface of a laminate and a plating layer provided on the base electrode layer. The base electrode layer is often a sintered body layer formed by baking a conductive paste comprising conductive powder such as Cu and Ni, glass powder, and an organic material. Here, since the thickness of the plating layer is extremely thin, the thickness of the external electrode is influenced by the thickness of the base electrode layer.

For example, one way to make multilayer ceramic capacitors smaller and larger in capacity is to reduce the thickness of the external electrodes as much as possible and increase the volume of the laminate that exhibits capacitance. For this purpose, it is necessary to reduce the thickness of the base electrode layer. On the other hand, if the base electrode layer is made thinner, there is a possibility that moisture may easily enter from the outside. The glass powder in the conductive paste is added to improve the sinterability of the conductive powder and to suppress the intrusion of moisture from the outside, that is, to obtain a base electrode layer with high moisture resistance.

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

International Publication No. 2017/057246

By the way, the borosilicate glass composition contains three-coordinated B and four-coordinated B. B in a borosilicate glass composition containing an alkaline earth metal element tends to be three-coordinated. If this tricoordinate B increases, there is a possibility that the moisture resistance of the base electrode layer formed by baking the conductive paste may decrease. However, Patent Document 1 does not mention anything about the ratio of 3-coordinated B to 4-coordinated B in a borosilicate-based glass composition, and the relationship between that ratio and moisture resistance.

The purpose of this disclosure is to focus on the coordination number of B, and to provide a conductive paste that can obtain a base electrode layer with high moisture resistance by baking, and an external electrode including a base electrode layer formed using the conductive paste. The object of the present invention 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 includes a borosilicate glass composition. When the amount of elements contained in the borosilicate glass composition is expressed in mol%, the amount of 4-coordinate B is C _B4 , the amount of 3-coordinate B is C _B3 , C _B4 The abundance ratio R B4 of four _- coordinated B expressed as /(C _B4 +C _B3 ) satisfies 0.35≦R _B4 ≦0.80.

A laminated electronic component according to this disclosure includes a laminated body including a plurality of laminated dielectric layers and a plurality of internal electrode layers, and a laminated body formed at mutually different positions on the outer surface of the laminated body, and a plurality of internal electrode layers. It includes 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 elements contained in the borosilicate glass composition is expressed in mol%, the amount of 4-coordinate B is C _B4 , the amount of 3-coordinate B is C _B3 , C _B4 The abundance ratio R B4 of four _- coordinated B expressed as /(C _B4 +C _B3 ) satisfies 0.35≦R _B4 ≦0.80.

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

1 is a schematic diagram of a conductive paste 1 which is an embodiment of a conductive paste according to this disclosure. This is an actual measurement example of an NMR spectrum focusing on B of a borosilicate glass composition. These are the results of signal separation performed by simulation of the NMR spectrum focusing on B of the borosilicate glass composition. 1 is a cross-sectional view of a multilayer ceramic capacitor 100 that is an embodiment of a multilayer electronic component according to this disclosure. FIG. 3 is a cross-sectional view for explaining the fine structure of the first base electrode layer 14a ₁ of the first external electrode 14a of the multilayer ceramic capacitor 100. This is a scanning transmission X-ray microscope (hereinafter sometimes abbreviated as STXM) spectrum obtained from a reference material in which C _B4 in B is known. It is a graph showing the relationship between the A/B ratio and C _B4 of the STXM spectrum obtained from a reference material in which C _B4 in B is known.

The features of this disclosure will be explained with reference to the drawings. In the embodiments of the multilayer electronic component shown below, the same or common parts are denoted by the same reference numerals in the figures, and the description thereof may not be repeated.

-Embodiment of conductive paste-
A conductive paste 1 showing an embodiment of the conductive paste according to this disclosure will be described using FIGS. 1 to 3.

<Composition of conductive paste>
FIG. 1 is a schematic diagram of a 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 single metal such as Cu or Ni, but also a Cu alloy or a Ni alloy.

Further, at least a portion 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 lower melting points than Cu and Ni. Therefore, the conductive powder 2 having the above structure can lower the sintering temperature.

Furthermore, at least a portion of the surface of the conductive powder 2 may be covered with an organic layer. In this case, effects such as steric hindrance repulsion or electrostatic repulsion can be obtained due to the presence of the organic layer, for example. As a result, even if the conductive powder 2 is fine particles, 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 circular diameter obtained from image analysis of a scanning electron microscope (hereinafter sometimes abbreviated as SEM) observation image of the conductive powder 2. And so. The median diameter of the equivalent yen diameter is the particle diameter (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.

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

The organic material 4 includes a binder component including a resin and an organic solvent, and additives including a dispersant, a rheology control agent, and the like. These components can be appropriately selected from materials commonly used as organic materials for conductive pastes.

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

When the amount of elements contained in the borosilicate glass composition is expressed in mol%, the amount of 4-coordinate B is C _B4 , the amount of 3-coordinate B is C _B3 , C _B4 The abundance ratio R B4 of four-coordinated B expressed _as /(C _B4 +C _B3 ) satisfies 0.35≦R _B4 ≦0.80.

The amount of 4-coordinated B contained in B of the borosilicate glass composition C _B4 and the amount of 3-coordinated B C _B3 are measured by nuclear magnetic resonance (hereinafter abbreviated as NMR). (There is a)

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

Assuming that B in the borosilicate glass composition includes 4-coordinated B and 3-coordinated B, the ratio between the amount of 4-coordinated B, C _B4 , and the amount of 3-coordinated B, C _B3 , is changed. By doing so, the NMR simulation spectrum at each ratio was calculated (solid line). Then, by performing fitting with the measured example of the spectrum shown in FIG. 2 and finding the ratio that maximizes the matching rate, the signal originating from the 4-coordinate B (dotted chain line) and the 3-coordinate B ( Separation from the signal originating from the dotted line) was performed.

Here, fitting was performed in the chemical shift range of -40 ppm to 50 ppm. The ratio between the amount of 4-coordinated B, C _B4 , and the amount of 3-coordinated B, C _B3 , was calculated from the area intensity of each signal after subtracting the background signal.

For example, the coincidence rate between the measured example of the NMR spectrum shown in Figure 2 and the simulation result derived from B shown in Figure 3 (solid line) is 97% or more in the chemical shift range of -40 ppm to 50 ppm. there were. Then, the amount C _B4 of four-coordinated B was 38 mol%, and the amount C _B3 of three-coordinated B was 62 mol%.

When the abundance ratio R _B4 of four-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 between B and O within the glass network structure is stabilized. Therefore, the elution of B in the borosilicate glass composition due to moisture contained in the environment is suppressed.

Note that the higher the abundance ratio R _B4 of four-coordinated B, the greater the above effect, but when R _B4 exceeds 0.80, the stability as a glass composition decreases. Therefore, the abundance ratio R _B4 of four-coordinated B substantially satisfies 0.35≦R _B4 ≦0.80.

Since the conductive paste 1 according to this disclosure includes the glass powder 3 having the above characteristics, the base electrode obtained by baking the conductive paste 1 can have high moisture resistance.

The borosilicate glass composition contained in the glass powder 3 contains a first element A and a second element AE, where the amount of the first element A is C _A and the amount of the second element AE is C _AE 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. It is. In this case, the abundance ratio R _B4 of four-coordinated B can be easily adjusted.

It is preferable that the borosilicate glass composition contained in the glass powder 3 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-coordinate B, it is also possible to improve the deflection strength of a multilayer ceramic capacitor equipped with a base electrode obtained by baking the conductive paste 1. can.

-Embodiment of laminated electronic component-
A multilayer ceramic capacitor 100 showing an embodiment of the multilayer electronic component according to this disclosure will be described using FIGS. 4 and 5. FIG.

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

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

The dielectric layer 11 has a plurality of crystal grains containing, for example, a BaTiO ₃ -based perovskite 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 compound is replaced by Re ³⁺ , which is a rare earth element ion. BaTiO ₃ -based perovskite compounds include BaTiO ₃ and those in which at least one of Ba ²⁺ and Ti ⁴⁺ of BaTiO ₃ is replaced with other ions such as Ca ²⁺ and Zr ⁴⁺ . Can be mentioned.

The first internal electrode layer 12a includes a counter electrode portion that faces the second internal electrode layer 12b through the dielectric layer 11, and a lead-out portion from the counter electrode portion to the first end surface 13a of the laminate 10. and an electrode section. The second internal electrode layer 12b includes a counter electrode portion that faces the first internal electrode layer 12a through the dielectric layer 11, and a lead-out portion from the counter electrode portion to the second end surface 13b of the laminate 10. and an electrode section.

One capacitor is formed by the first internal electrode layer 12a and the second internal electrode layer 12b facing each other with the dielectric layer 11 in between. The multilayer ceramic capacitor 100 can be said to have 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, etc., or an alloy containing the metal can be used. The internal electrode layer 12 may further include dielectric particles called a common material (not shown) as described later. The common material is added to the internal electrode layer paste used to form the internal electrode layer 12, and is discharged to the dielectric layer 11 side when the laminate 10 is fired, but a part of it is added to the internal electrode layer paste. It may remain in layer 12. The co-material is added to bring the sintering shrinkage characteristics of the internal electrode layer 12 closer to the sintering shrinkage characteristics of the dielectric layer 11 when the laminate 10 is fired.

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 extends from the first end surface 13a to the first main surface and the first main surface. 2 and the first side and second side. 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 extends from the second end surface 13b to the first main surface and the first main surface. 2 and the first side and second side.

The first external electrode 14a includes a first base electrode layer 14a ₁ and a first plating layer 14a ₂ disposed 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 layers (described below). 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 includes a second base electrode layer 14b ₁ and a second plating layer 14b ₂ disposed 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 fine structure 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 . The second base electrode layer 14b ₁ has the same structure as the first base electrode layer 14a ₁ , so further explanation will be omitted.

The sintered body layer of the first base electrode layer 14a ₁ includes the conductive region 15a ₁ and the 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 this disclosure, the conductive region 15a ₁ is a metal sintered body in which the conductive powder 2 included in the conductive paste 1 is sintered. Contains. Similarly, the glass region 16a ₁ contains a glass component derived from the glass powder 3, that is, a borosilicate glass composition. Note that 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 disposed on the first base electrode layer 14a ₁ , at least one selected from Ni, Cu, Ag, Au, Sn, etc. or an alloy containing the metal is used. be able to. The plating layer may be formed of a plurality of layers of different components. Preferably, there are two layers: a Ni plating layer and a Sn plating layer.

The Ni plating layer is disposed on the base electrode layer, and can prevent the base electrode layer from being eroded by solder when mounting the multilayer electronic component. The Sn plating layer is placed on the Ni plating layer. Since the Sn plating layer has good wettability with solder containing Sn, it is possible to improve mounting performance when mounting a multilayer electronic component. Note that these plating layers are not essential.

When the amount of elements contained in the borosilicate glass composition in the glass region _16a1 is expressed in mol%, the amount of 4-coordinated B is C _B4 , and the amount of 3-coordinated B is C _B3 . Then, the abundance ratio R B4 of four-coordinated B expressed 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 also has similar characteristics.

The amount C _B4 of four-coordinated B and the amount C _B3 of three-coordinated B contained in B of the borosilicate glass composition are measured using a scanning transmission X-ray microscope (STXM). The STXM is a device that detects transmitted signals when a finely focused X-ray beam is scanned relative to the sample by moving a thin sectioned sample. Transmission signal usually refers to transmitted X-ray intensity. Here, by taking the ratio of the transmitted X-ray intensity and the incident X-ray intensity, the absorption intensity can be easily obtained. That is, an STXM spectrum is obtained by obtaining a plurality of two-dimensional absorption images whose respective energy intensities are measured based on the measurement energy range and energy step conditions, 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 are obtained. Note that the energy step width may be changed within the measurement energy range. An STXM spectrum is obtained by superimposing the C obtained absorption images. By analyzing this STXM spectrum, information regarding the chemical bonding state of the sample can be obtained.

The measurement and analysis of the STXM spectrum will be further explained using 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 a light source (X-ray source), the photon energy (wavelength) of incident X-rays 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, absorption of X-rays increases above a certain threshold value, and this threshold value is the so-called absorption edge. Furthermore, when examining the X-ray absorption intensity in detail near this absorption edge, a unique structure appears in the absorption spectrum depending on the chemical bonding state of the element of interest. This unique structure is called an X-ray absorption fine structure (hereinafter sometimes 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 depending on the chemical bonding state of the element of interest.

By performing peak separation, it can be seen that the STXM spectrum of the K absorption edge of B includes peaks due to the π ^* bond and the σ ^* bond of the B—O coordination structure. The STXM spectrum in FIG. 6 includes a spire-shaped π ^* peak labeled Energy A near 194 eV, and a broad σ ^* peak labeled Energy B near 198 eV and Energy C near 203 eV. Note that the STXM spectrum in Figure 6 also includes other broad peaks, but in the analysis below, the π ^* peak originates from B in the 3-coordination (sp ² structure: BO ₃ ), and the σ ^* peak was derived from B with four coordination (sp ³ structure: BO ₄ ).

Here, in the three types of STXM spectra shown in FIG. 6, there is a first-order correlation between the A/B ratio, which is the ratio of the peak intensity of Energy A to the peak intensity of Energy B, and C _B4 . It turns out that there is.

FIG. 7 is a graph showing the relationship between the A/B ratio and C _B4 of STXM spectra 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 four-coordinated B expressed as C _B4 /(C _B4 +C _B3 ) can be calculated.

When the abundance ratio R _B4 of four-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 between B and O within the glass network structure is stabilized. Therefore, the elution of B in the borosilicate glass composition due to moisture contained in the environment is suppressed.

Note that the higher the abundance ratio R _B4 of four-coordinated B, the greater the above effect, but when R _B4 exceeds 0.80, the stability as a glass composition decreases. Therefore, the abundance ratio R _B4 of four-coordinated B substantially satisfies 0.35≦R _B4 ≦0.80.

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

The borosilicate glass composition contained in the glass region includes a first element A and a second element AE, where the amount of the first element A is C _A and the amount of the second element AE is C _AE . In this case, 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. It is. In this case, the abundance ratio R _B4 of four-coordinated B can be easily adjusted.

The borosilicate glass composition included in the glass region preferably has the above C _AE satisfying 9.4≦C _AE ≦47.1. In this case, in addition to being able to easily adjust the abundance ratio R _B4 of 4-coordinate B, it is also possible to improve the deflection strength of a multilayer ceramic capacitor equipped with a base electrode obtained by baking the conductive paste 1. can.

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

In addition, conductive pastes were prepared using glass powders from sample numbers 1 to 17, Cu powders with an average particle size of 0.5 μm confirmed through image analysis of SEM observation images, and organic materials. A multilayer ceramic capacitor as shown in FIG. 4 in which a base electrode layer of an external electrode was formed was fabricated. Note that the dielectric layer in the laminate of the multilayer ceramic capacitor is formed of a dielectric material containing a BaTiO ₃ -based perovskite compound, and the internal electrode layer is formed of Ni.

Using these multilayer ceramic capacitors, the abundance ratio of four-coordinated 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 sometimes abbreviated as PCBT). In addition, the deflection strength of the multilayer ceramic capacitor produced as described above was evaluated based on a deflection test method based on JIS standards.

NMR evaluation of the abundance ratio of 4-coordinated B in the borosilicate glass compositions contained in the glass powders of Sample No. 1 to Sample No. 20 was performed under the conditions shown in Table 1.

The abundance ratio of 4-coordinated 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 powder of sample number 1 to sample number 20. Evaluation by STXM was performed under the conditions shown in Table 2.

The moisture resistance of the multilayer ceramic capacitors having base electrode layers formed by baking conductive pastes containing glass powder of sample numbers 1 to 20 was evaluated under the conditions shown in Table 3.

Evaluation of the deflection strength of the multilayer ceramic capacitors having base electrode layers formed by baking conductive pastes containing glass powder of Sample No. 1 to Sample No. 20 was performed under the conditions shown in Table 4.

NMR evaluation results of the abundance ratio of 4-coordinated B in the borosilicate-based glass composition contained in the glass powder, STXM evaluation results of the abundance ratio of 4-coordinated B in the glass region of the base electrode layer, and The evaluation results of the moisture resistance of the multilayer ceramic capacitors are summarized in Table 5. In Table 5, sample numbers marked with * are samples that deviate from the conditions that define the conductive paste according to this disclosure.

In addition, the evaluation results of the deflection strength of multilayer ceramic capacitors excluding samples determined to be defective in the evaluation results of moisture resistance are as follows: The results are summarized in Table 6 together with the evaluation results of the abundance ratio of B in the coordination.

In addition, the NMR evaluation results of the abundance ratio of 4-coordinated B in the borosilicate glass composition contained in the glass powder in Tables 5 and 6, and the presence of 4-coordinated B in the glass region of the base electrode layer. The STXM evaluation result of the ratio is the average value of the measurement results obtained from each of the three samples. That is, the characteristic numerical range of the four-coordinate B in this disclosure is defined from the average value of a plurality of measurement results. In other words, whether 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 target with the numerical range in this disclosure.

NMR evaluation results of the abundance ratio of 4-coordinated B in the borosilicate glass composition contained in the glass powder, and the glass possessed by the base electrode layer formed by baking the conductive paste using the glass powder. It was confirmed that the evaluation results of the abundance ratio of 4-coordinated B in the region were consistent with the NMR evaluation results. That is, during baking of the conductive paste, the amount of B and the chemical bonding state in the borosilicate glass composition do not essentially change. In other words, the abundance ratio of 4-coordinated B in the glass region of the base electrode layer in the state of a multilayer ceramic capacitor is equal to the abundance ratio of 4-coordinated B in the borosilicate glass composition contained in the glass powder included in the conductive paste. It can be estimated based on the abundance ratio of B.

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

The embodiments disclosed in this specification are illustrative, and the invention according to this disclosure is not limited to the above embodiments. That is, the scope of the invention according to this disclosure is indicated by the claims, and it is intended that the meaning equivalent to the claims and all changes within the range are included. Furthermore, various applications and modifications can be made within the above range.

For example, various applications and modifications can be made within the scope of the present invention with respect to the number of dielectric layers and internal electrode layers constituting the laminate, the materials of the dielectric layers and internal electrode layers, and the like. Further, although a multilayer ceramic capacitor is illustrated as an example of a multilayer electronic component, the invention according to this disclosure is not limited thereto, and can also be applied to a capacitor element formed inside a multilayer substrate.

Furthermore, the number and location of external electrodes are not limited to the embodiments disclosed in this specification. That is, a plurality of external electrodes may be formed at different positions on the outer surface of the laminate and electrically connected to the internal electrode layer.

1 Conductive paste 2 Conductive powder 3 Glass powder 4 Organic material 100 Multilayer ceramic capacitor 10 Laminated body 11 Dielectric layer 12 Internal electrode layer 13a First end surface 13b Second end surface 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 (7)

A conductive powder containing at least one element selected from Cu and Ni, a borosilicate glass composition, and an organic material,
When the amount of elements contained in the borosilicate glass composition is expressed in mol%, 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 four-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. The conductive paste according to claim 1, comprising : The conductive paste according to claim 1 or 2 , 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. The conductive paste according to any one of claims 1 to 3 , wherein at least a part of the surface of the conductive powder is covered with an organic layer. The conductive paste according to any one of claims 1 to 4 , wherein the conductive powder has an average particle size of 1 μm or less. a laminate including a plurality of laminated dielectric layers and a plurality of internal electrode layers; and a plurality of laminates formed at different positions on the outer surface of the laminate and electrically connected to the internal electrode layers. Equipped with an external electrode of
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%, the amount of 4-coordinated B is C _B4 and the amount of 3-coordinated B is C _B3 , C _B4 / A multilayer electronic component in which the abundance ratio R _B4 of four-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. The laminated electronic component according to claim 6 , comprising :