KR20210052252A - Conductive Paste and Multilayer Type Electronic Component - Google Patents

Abstract

A conductive paste capable of obtaining a lower electrode layer having high adhesion to a laminate at a low baking temperature while being dense is provided.
The conductive paste 1 contains a conductive powder 2 containing at least one element selected from Cu and Ni, a glass powder 3 and an organic material 4. The glass powder (3) contains a borosilicate-based glass composition having a softening point of 455°C to 650°C, and the mass spectrum obtained by mass spectrometry of the gas generated when the mixture of the glass powder (3) and C powder is heated at elevated temperature is 470 It has a gas generation peak of 44 mass numbers at a temperature of not less than 680°C and not more than 680°C.

Description

Conductive Paste and Multilayer Type Electronic Component

The present disclosure relates to a multilayer electronic component including a conductive paste including glass powder, and an external electrode formed by using the same.

An external electrode of a multilayer electronic component such as a multilayer ceramic capacitor generally includes a lower electrode layer formed on the surface of the multilayer body and a plating layer applied on the lower electrode layer. The lower 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 lower electrode layer.

For example, as a means for increasing the size and capacity of the multilayer ceramic capacitor, the thickness of the external electrode is made as thin as possible, and the volume of the laminate that expresses the electrostatic capacitance is increased. To do this, it is necessary to make the thickness of the lower electrode layer thin. On the other hand, if the lower electrode layer is made thin, there is a fear that moisture can easily enter from the outside. The glass powder in the conductive paste is added in order to improve the sinterability of the conductive powder and to obtain a dense lower electrode layer capable of suppressing the intrusion of moisture from the outside.

As a component of the glass powder, a borosilicate-based glass composition containing oxides of B oxide and Si as mesh-forming oxides and oxides of alkaline earth metal elements such as Ba, Ca, and Sr as modified oxides is often used. As an example of a conductive paste containing glass powder in which the borosilicate-based glass composition is used, the conductive paste described in International Publication No. WO2014/175013 (Patent Document 1) can be mentioned. The conductive paste disclosed in Patent Document 1 is baked in a laminate at 800°C to 900°C.

International Publication WO2014/175013

The conductive paste disclosed in Patent Document 1 is baked at a high temperature as described above. Therefore, when the lower electrode layer is cooled from the baking temperature to room temperature, the degree of shrinkage is large. As a result, a large stress is applied to the laminate, and there is a fear that cracks may occur. That is, in order to suppress the occurrence of cracks, it is necessary to lower the baking temperature of the conductive paste and to reduce the degree of shrinkage during cooling of the lower electrode layer. On the other hand, when the baking temperature is lowered, the organic material in the conductive paste remains without sufficiently burning or decomposing, and there is a concern that densification of the lower electrode layer may be inhibited. In addition, although it is densified, there is a concern that the bonding property between the laminate and the lower electrode layer is deteriorated.

An object of the present disclosure is to provide a multilayer electronic component including a conductive paste capable of obtaining a lower electrode layer having high adhesion to a laminate at a low baking temperature and having high adhesion to a laminate, and an external electrode including a lower electrode layer formed by using the same.

The conductive paste according to the present disclosure contains 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-based glass composition having a softening point of 455°C or more and 650°C or less. In addition, a mass spectrum obtained by mass spectrometry of a gas generated when the mixture of glass powder and C powder is heated at elevated temperature has a gas generation peak of 44 masses at 470°C or more and 680°C or less.

A stacked electronic component according to the present disclosure includes a stacked body including a plurality of stacked dielectric layers and a plurality of internal electrode layers, and a plurality of external electrodes formed at different positions on the outer surface of the stacked body and electrically connected to the internal electrode layers. do. In addition, the external electrode includes a lower electrode layer formed by baking a conductive paste according to the present disclosure.

The conductive paste according to the present disclosure can obtain a lower electrode layer that is dense at a low baking temperature and has high adhesion to a laminate. In addition, the multilayer electronic component according to the present disclosure may include an external electrode including the lower electrode layer formed by baking a conductive paste according to the present disclosure.

1 is a schematic diagram of a conductive paste 1 which is an embodiment of a conductive paste according to the present disclosure.
FIG. 2 is a schematic diagram for explaining an estimated mechanism for acceleration of combustion of the organic material 4 by the glass powder 3.
3 is a graph (Ellingham diagram) showing the relationship between the standard free energy and temperature of the oxides of Cu, Ni, Co, and C.
4 is a cross-sectional view of a multilayer ceramic capacitor 100 as an embodiment of a multilayer electronic component according to the present disclosure.
5 is a cross-sectional view illustrating a microstructure _{of the first lower electrode 14a 1} of the first external electrode 14a of the multilayer ceramic capacitor 100.

Features of the present disclosure will be described with reference to the drawings. On the other hand, in the embodiments of the multilayer electronic component shown below, the same or common portions are denoted by the same reference numerals in the drawings, and the description may not be repeated.

-Embodiment of conductive paste-

A conductive paste 1 showing an embodiment of a conductive paste according to the present disclosure will be described with reference to FIGS. 1 to 3.

<Configuration of conductive paste>

1 is a schematic diagram of a conductive paste 1. The conductive paste 1 contains a conductive powder 2 and 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 Cu or Ni metal alone, but also Cu alloy or Ni alloy.

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

Moreover, at least a part of the surface of the conductive powder 2 may be covered with an organic material layer. In this case, effects such as steric hindrance repulsion or electrostatic repulsion are obtained, for example, by the presence of the organic material layer. 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.

And it is preferable that the average particle diameter of the electroconductive powder 2 is 1 micrometer or less. The average particle diameter of the conductive powder 2 is the equivalent circle diameter obtained from the image analysis on the observation of the scanning electron microscope (Scanning Electron Microscope: hereinafter, sometimes abbreviated as SEM) of the conductive powder 2 I made it the median diameter. _{The median diameter of the equivalent circle diameter is a particle diameter (D 50} ) at which the integrated% becomes 50% in the distribution curve of the integrated% with respect to the particle diameter. In this case, the conductive powder 2 can lower the sintering temperature.

The glass powder 3 is a glass powder according to the present disclosure. The characteristics of this glass powder 3 will be described later. On the other hand, in Fig. 1, the conductive powder 2 and the glass powder 3 are schematically depicted in a spherical shape, but the shape of each powder is not the only one. For example, the conductive powder 2 may contain a flat conductive powder. The glass powder 3 may also contain the glass powder of an irregular shape.

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

The glass powder 3 contains a borosilicate-based glass composition. The borosilicate-based glass composition is a glass composition containing a B oxide and a Si oxide as a mesh-forming oxide, and containing an alkali metal element oxide, an alkaline earth metal element oxide, and the like as a modified oxide. And the softening point of the borosilicate-based glass composition contained in the glass powder 3 is 455°C or more and 650°C or less.

The measurement of the softening point of the object to be measured is performed by a thermogravimeter-differential thermal analyzer (hereinafter, sometimes abbreviated as TG-DTA). Measurement conditions will be described later.

That is, the softening point of the borosilicate-based glass composition contained in the glass powder 3 is lower than that of the conventional borosilicate-based glass composition. Therefore, when the lower electrode layer formed by baking of the conductive paste 1 containing the glass powder 3 is cooled from the baking temperature to room temperature, the degree of shrinkage is small. As a result, the stress applied to the laminate is reduced, and the occurrence of cracks is suppressed. However, as described above, when the baking temperature is lowered, the organic material in the conductive paste remains without being sufficiently burned or decomposed, and there is a concern that densification of the lower electrode layer may be inhibited.

Therefore, in the conductive paste 1 according to the present disclosure, the organic material 4 in the conductive paste 1 is sufficiently burned by the glass powder 3. Specifically, the mass spectrum obtained by mass spectrometry of the gas generated when the mixture of the glass powder 3 and the C powder is heated at elevated temperature has a mass number of 44, that is, CO ₂ gas generation peak at 470°C or more and 680°C or less. Has a characteristic. In other words, the glass powder 3 softens and flows in the above temperature range to contact the residue of the organic material 4, thereby supplying O from the constituents of the glass fluid, accelerating the combustion of the residue of the organic material 4, and have.

On the other hand, the softening point of the glass composition is a temperature at which the viscosity η (Pa·s) of the glass composition is 6.65 or less in logη, and if it is a temperature close to the softening point, the glass composition is softened and fluidized even if it is below the temperature of the softening point. Therefore, the softening point of the borosilicate-based glass composition contained in the glass powder 3 may be higher than the peak temperature of _{CO 2 gas generation.}

The above will be further described with reference to FIG. 2. 2 is a schematic diagram for explaining an estimated mechanism for acceleration of combustion of the organic material 4 by the glass powder 3. Fig. 2(A) shows a state in which the glass powder 3 and the C component 5 corresponding to the residue of the organic material 4 are mixed at a temperature slightly lower than the softening point. However, as described above, since the glass powder 3 starts softening flow even at this stage, the C component 5 may be in a state surrounded by the glass powder 3 that is softening and flowing.

Fig. 2(B) shows a state in which the glass powder 3 is softened at a temperature slightly higher than the softening point to become a glass fluid 3f, and is in contact with the C component 5. On the other hand, in Fig. 2(B), a state in which the C component 5 is surrounded by the glass fluid 3f is shown, but the C component 5 and the glass fluid 3f may be partially in contact. In this state, O is supplied from the constituent components of the glass fluid 3f.

2(C) is a bubble of a gas containing _{CO 2} in the glass fluid 3f by burning the C component 5 that received O at the temperature in the state shown in FIG. 2(B) and at a higher temperature. (5g) shows the produced state. However, in this state, the viscosity of the glass fluid 3f is not lowered so that the gas bubbles 5g burst, and the gas bubbles 5g remain in the glass fluid 3f.

2(D) shows that the viscosity of the glass fluid 3f is lowered at a temperature higher than the temperature in the state shown in FIG. 2(B), so that a bubble of gas (5g) bursts to cause CO from the glass fluid 3f. _It shows the state in which the gas containing 2 came out. As a result, the gas generation peak of _{CO 2} is detected in the mass spectrometry of the gas generated when the object to be measured is heated at elevated temperature.

On the other hand, as described above, the mechanism is reasonably estimated, but there is a possibility that other factors may be involved. That is, it should be noted that the condition of the conductive paste in the present disclosure is not necessarily explained only by the above mechanism.

The mass spectrometry of the gas generated during heating of the object to be measured is performed by a thermogravimetry-mass spectrometer (hereinafter, sometimes abbreviated as TG-MS). Measurement conditions will be described later.

Since the conductive paste 1 according to the present disclosure contains the glass powder 3 having the above characteristics, the organic material 4 in the conductive paste 1 can be sufficiently burned even at a low baking temperature. As a result, the necking between the conductive powders 2 is not inhibited by residual organic components derived from the organic material 4, and sintering of the conductive powder 2 is promoted. Therefore, densification of the lower electrode layer is promoted, and a decrease in the bonding property between the laminate and the lower electrode layer is suppressed.

It is preferable that the borosilicate-based glass composition contained in the glass powder 3 contains 36 mol% or more and 68 mol% or less of at least one type of first element (M1) serving as a modified oxide among the constituent elements excluding oxygen. Here, the modified oxide in the present disclosure is a concept indicating oxides other than the mesh-forming oxide (Si oxide and B oxide) in the glass composition. That is, the modified oxide in the present disclosure also includes an Al oxide called an intermediate oxide in the glass composition. In this case, the softening point of the borosilicate-based glass composition can be easily adjusted to 455°C or more and 650°C or less.

In addition, it is preferable that the first element (M1) contains at least one element selected from Li, Na and K. In this case, it is possible to more easily adjust the softening point of the borosilicate-based glass composition.

Borosilicate based glass composition contained in the glass powder 3 has a first element (M1) standard generated free energy of an oxide of at least the softening point (ΔG _M °) is greater than the standard production of CO ₂ free energy (ΔG _C °) of It is preferable to contain 1.5 mol% or more and 6.5 mol% or less of at least 1 type of 2nd element (M2) which becomes an oxygen supply oxide. On the other hand, this ratio is for the constituent elements excluding oxygen.

That is, the second element (M2) in the glass fluid 3f in a state in which the above-described glass powder 3 is softened to become a glass fluid 3f, and is in contact with the C component 5 (see Fig. 2(B)). ), O is supplied. In this case, in the mass spectrum of the mixture of the glass powder 3 and the C powder by TG-MS, the _{peak of CO 2} gas generation can be easily generated at 470°C or more and 680°C or less.

The above will be further described with reference to FIG. 3. 3 is a graph showing the relationship between the standard free energy and temperature of oxides of Cu, Ni, Co, and C, a so-called Elling sensitivity. The element alone is stable in the region below the line indicating the relationship between the standard free energy (ΔG°) and temperature of the oxide, and the oxide is stable in the upper region.

That is, the Elling sensitivity is expressed by relating the stability of oxides of various elements to the equilibrium oxygen partial pressure. From the Elling sensitivity, it is possible to know which reducing agent should be applied at what temperature to reduce the oxide of a predetermined element, and whether or not the metal is oxidized under a predetermined partial pressure of oxygen.

Looking at the line (solid line) related to the oxidation of C and the line (broken line) related to the oxidation of Cu shown in Fig. 3, the softening point of the glass powder 3 or higher, that is, 455°C or higher, and related to the oxidation of C The line is located in a region below the line related to the oxidation of Cu. Therefore, in the region between the line related to the oxidation of Cu and the line related to the oxidation of C, Cu is stable in Cu alone, and C is stable _{in CO 2.} That is, when Cu is included as the second element (M2) in the first element (M1), the Cu oxide of the borosilicate-based glass composition is reduced under the temperature and oxygen partial pressure in the region, and oxygen required to burn C is removed. Can supply.

In Fig. 3, a line related to the oxidation of Co (dashed-dotted line) and a line related to the oxidation of Ni (double-dotted chain line) are also shown. In the same manner as described above, the line related to the oxidation of C and above the softening point of the glass powder 3 is located in a region below the line related to the oxidation of Co and the line related to the oxidation of Ni. Therefore, even when Co and Ni are contained as the second element (M2) in the first element (M1) as the modified oxide of the borosilicate-based glass composition, the same action can be exhibited.

That is, when the second element M2 is contained in the first element M1, even if the baking temperature of the conductive paste 1 is low, the organic material 4 in the conductive paste 1 can be effectively burned. In other words, in the above case, in the mass spectrum by TG-MS of the mixture of the glass powder 3 and the C powder, the gas generation peak of _{CO 2 can be easily generated at 470° C. or more and 680° C. or less.}

For example, when at least a part of the surface of the conductive powder 2 is covered with an organic material layer, the conductive paste 1 before baking is more than when the conductive powder 2 is not covered with an organic material layer. It becomes something containing an organic material. That is, the organic material in the conductive paste remains without being sufficiently burned or decomposed, and it is easy to inhibit the densification of the lower electrode layer.

However, as described above, when the second element M2 is contained in the first element M1, the organic material 4 in the conductive paste 1 can be effectively burned even when the baking temperature of the conductive paste 1 is low. have. This effect becomes particularly remarkable when the average particle diameter of the conductive powder ₂ from which CO 2 is difficult to escape during baking of the conductive paste 1 is 1 µm or less.

The second element M2 is not limited to Cu, Co, and Ni shown above. On the other hand, when the second element (M2) is at least one element selected from Cu, Co, and Ni, it is possible to more easily adjust the softening point of the borosilicate-based glass composition.

-Embodiment of a laminated electronic component-

A multilayer ceramic capacitor 100 showing an embodiment of a multilayer electronic component according to the present disclosure will be described with reference to FIGS. 4 and 5.

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

The plurality of internal electrode layers 12 have a first internal electrode layer 12a and a second internal electrode layer 12b. The stacked body 10 includes a first main surface and a second main surface facing in the stacking direction, a first side and a second side facing in a width direction orthogonal to the stacking direction, and a longitudinal direction orthogonal to the stacking direction and the width direction. It has a first cross-section 13a and a second cross-section 13b facing each other.

The dielectric layer 11 has a plurality of crystal grains including, for example, a BaTiO _{3 -based perovskite compound.} Examples of the 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 an ion of a rare earth element. In addition, BaTiO ₃ -based perovskite compounds include BaTiO ₃ and BaTiO ₃ in which at least one of Ba ²⁺ and Ti ⁴⁺ is substituted with other ions such as ^{Ca 2+} and Zr ^4+. have.

The first internal electrode layer 12a includes a second internal electrode layer 12b and a counter electrode portion facing each other through the dielectric layer 11, and from the counter electrode portion to the first end surface 13a of the stacked body 10. It includes a lead electrode part. The second internal electrode layer 12b includes the first internal electrode layer 12a and the counter electrode portion facing each other through the dielectric layer 11, and from the counter electrode portion to the second end surface 13b of the stacked body 10. It includes a lead electrode part.

The first internal electrode layer 12a and the second internal electrode layer 12b face each other through the dielectric layer 11 to form one capacitor. In the multilayer ceramic capacitor 100, a plurality of capacitors may be connected in parallel through a first external electrode 14a and a second external electrode 14b to be described later.

As a conductive material constituting the internal electrode layer 12, at least one metal selected from Ni, Cu, Ag, and Pd, or an alloy containing the metal may be used. The internal electrode layer 12 may further contain dielectric particles called common materials (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, and a part of the material remains in the internal electrode layer 12. There are cases. The common material is added to make the sintering shrinkage property of the internal electrode layer 12 close to the sintering shrinkage property of the dielectric layer 11 during firing of the laminate 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 stack 10 so as to be electrically connected to the first internal electrode layer 12a, and the first main surface and the second main surface from the first end surface 13a. And it extends to the first side and the second side. The second external electrode 14b is formed on the second end surface 13b of the stack 10 so as to be electrically connected to the second internal electrode layer 12b, and the first main surface and the second main surface from the second end surface 13b. And it extends to the first side and the second side.

The first external electrode 14a has a first lower electrode layer 14a ₁ and a first plating layer 14a ₂ disposed on the first lower electrode layer 14a ₁ . The first lower electrode layer 14a ₁ has a sintered body layer (described later) formed by baking the conductive paste 1 according to the present disclosure. Similarly, the second external electrode 14b has a second lower electrode layer 14b ₁ and a second plating layer 14b ₂ disposed on the second lower electrode layer 14b ₁ . The second lower electrode layer 14b ₁ also has a sintered body layer (described later) formed by baking the conductive paste 1 according to the present disclosure.

5 is a cross-sectional view illustrating a microstructure of the first lower electrode layer 14a _1. Since the second lower electrode layer 14b ₁ has the same structure as the first lower electrode layer 14a ₁ , the following description will be omitted. The sintered body layer of the first lower electrode layer 14a ₁ includes a conductor region 15a ₁ and a glass region 16a ₁ . The conductor region 15a ₁ includes a metal sintered body in which the conductive powder 2 included in the conductive paste 1 is sintered. The glass region 16a ₁ contains a glass component derived from the glass powder 3. On the other hand, the sintered compact layer may be formed in multiple layers with different components.

As the metal constituting the first plating layer 14a ₂ disposed on the first lower electrode layer 14a ₁ , at least one selected from Ni, Cu, Ag, Au, and Sn, or an alloy containing the metal may be used. have. The plating layer may be formed of a plurality of layers of different components. Preferably, they are two layers of a Ni plated layer and a Sn plated layer.

The Ni plating layer is disposed on the lower electrode layer, and when mounting the multilayer electronic component, it is possible to prevent the lower electrode layer from being eroded by solder. The Sn plating layer is disposed on the Ni plating layer. Since the Sn-plated layer has good wettability with a solder containing Sn, it is possible to improve the mountability when mounting a multilayer electronic component. On the other hand, this plating layer is not essential.

The multilayer ceramic capacitor 100 according to the present disclosure may include an external electrode including a lower electrode layer formed by baking of the conductive paste 1, in which densification is promoted and deterioration of adhesion to the laminate is suppressed.

-Experimental example-

The conductive paste according to the present disclosure will be described in more detail based on the following experimental examples. These experimental examples are also intended to give a basis for defining the conditions or more preferable conditions of the conductive paste according to the present disclosure. In the experimental example, glass powders of Sample Nos. 1 to 20 were prepared, and evaluation of the softening point by TG-DTA, and evaluation of the generation behavior _{of CO 2 gas in a mixture of the glass powder and C powder by TG-MS were performed.} .

In addition, a conductive paste was prepared using glass powder of Sample No. 1 to Sample No. 20, Cu powder having an average particle diameter of 0.5 μm, and an organic material, and a lower electrode layer of the external electrode was formed using them, as shown in FIG. 4. A ceramic capacitor was built. On the other hand, the dielectric layer in the laminate of the multilayer ceramic capacitor is formed of _{a dielectric material containing a BaTiO 3} type perovskite compound, and the internal electrode layer is formed of Ni. Using these multilayer ceramic capacitors, evaluation of the bonding property between the lower electrode layer of the external electrode and the laminate and the density evaluation of the lower electrode layer were performed.

Evaluation of the softening point of the glass powders of Sample No. 1 to Sample No. 20 by TG-DTA was performed under the conditions shown in Table 1.

_{The evaluation of the generation behavior of CO 2} gas in the mixture of the glass powder and C powder of Sample No. 1 to Sample No. 20 by TG-MS was performed under the conditions shown in Table 2.

Evaluation of the bonding property between the lower electrode layer and the laminate in the multilayer ceramic capacitor in which the lower electrode layer of the external electrode was formed by baking the conductive paste containing the glass powder of Sample Nos. 1 to 20 was conducted under the conditions shown in Table 3. .

Evaluation of the density of the lower electrode layer in the multilayer ceramic capacitor in which the lower electrode layer of the external electrode was formed by baking the conductive paste containing the glass powder of Sample Nos. 1 to 20 was performed under the conditions shown in Table 4.

Table 5 shows the softening point evaluation results, the CO ₂ gas generation behavior evaluation results, the bonding evaluation results of the lower electrode layer and the laminate, and the density evaluation results of the lower electrode layer.

In Table 5, a sample number marked with * is a sample that deviates from the conditions defining the conductive paste according to the present disclosure.

As described above, in the borosilicate-based glass composition of Sample No. 2, for example, B oxide and Si oxide are mesh-forming oxides, and each oxide of Ba, Ca, Al, Mn, Cu, and Ti is regarded as a modified oxide. That is, the ratio of the first element (M1) is that the total ratio of each element of Ba, Ca, Al, Mn, Cu, and Ti among the constituent elements of the borosilicate-based glass composition excluding O is expressed in mol%. As shown in Table 5, it was confirmed that the bonding property of the lower electrode layer and the laminate and the density of the lower electrode layer were good in each sample that satisfies the conditions for defining the conductive paste according to the present disclosure.

Embodiments disclosed in this specification are exemplary, and the invention according to the present disclosure is not limited to the above embodiments. That is, the scope of the invention according to the present disclosure is indicated by the claims, and it is intended that the meanings equivalent to the claims and all changes within the scope are included. In addition, various applications and modifications can be applied within the above range.

For example, various applications and modifications can be made within the scope of the present invention regarding the number of layers of the dielectric layer and the internal electrode layer constituting the laminate, the material of the dielectric layer and the internal electrode layer, and the like. In addition, a multilayer ceramic capacitor was exemplified as a multilayer electronic component, but the invention according to the present disclosure is not limited thereto, and may be applied to a capacitor element formed inside a multilayer substrate.

Moreover, the number and position of external electrodes are 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 laminate and electrically connected to the internal electrode layer.

1: conductive paste
2: conductive powder
3: glass powder
3f: glass fluid
4: organic ingredients
5: C component
5g: bubbles of gas
100: multilayer ceramic capacitor
10: laminate
11: dielectric layer
12: internal electrode layer
13a: first cross section
13b: second cross section
14a: first external electrode
14a ₁ : first lower electrode layer
14a ₂ : 1st plating layer
14b: second external electrode
14b ₁ : second lower electrode layer
14b ₂ : second plating layer
15a ₁ : conductive region
16a ₁ : glass area
M1: first element
M2: second element
ΔG°: the standard free energy produced by the oxide
ΔG _M °: the standard free energy produced by the oxide of the second element
ΔG _C °: Standard free energy generated in _{CO 2}

Claims (9)

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-based glass composition having a softening point of 455° C. or more and 650° C. or less, and a mass spectrum obtained by mass spectrometry of a gas generated when the mixture of the glass powder and C powder is heated at elevated temperature. ) Is a conductive paste having a gas generation peak having a mass number of 44 at 470°C or more and 680°C or less. The method of claim 1,
The conductive paste, wherein the borosilicate-based glass composition contains 36 mol% or more and 68 mol% or less of at least one type of first element that becomes a modified oxide among constituent elements excluding oxygen. The method of claim 2,
The first element is a conductive paste containing at least one element selected from Li, Na and K. The method according to claim 2 or 3,
The borosilicate-based glass composition contains 1.5 mol% or more of 6.5 mol% or more of at least one second element that becomes an oxygen-supplying oxide whose standard free energy of oxides above the softening point of the first element is greater than the standard free energy of CO ₂ A conductive paste containing% or less. The method of claim 4,
The second element is a conductive paste containing at least one element selected from Cu, Co, and Ni. The method according to any one of claims 1 to 3,
A conductive paste in which 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 method according to any one of claims 1 to 3,
A conductive paste in which at least a part of the surface of the conductive powder is covered with an organic material layer. The method according to any one of claims 1 to 3,
The conductive paste, wherein the average particle diameter of the conductive powder is 1 µm or less. A laminate comprising a plurality of stacked dielectric layers and a plurality of internal electrode layers, and a plurality of external electrodes formed at different positions on an outer surface of the laminate and electrically connected to the internal electrode layer,
The multilayer electronic component, wherein the external electrode includes a lower electrode layer formed by baking the conductive paste according to any one of claims 1 to 3.

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