KR102677064B1 - Conductive Paste and Multilayer Type Electronic Component - Google Patents

Abstract

A conductive paste capable of obtaining a dense lower electrode layer with high adhesion to a laminate at a low baking temperature 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 with a softening point of 455°C or more and 650°C or less, and the mass spectrum obtained by mass analysis of the gas generated when heating the mixture of the glass powder (3) and C powder at elevated temperatures is 470°C. It has a gas generation peak with a mass number of 44 above ℃ and below 680℃.

Description

Conductive Paste and Multilayer Type Electronic Component}

The present disclosure relates to a conductive paste containing glass powder and a multilayer electronic component including external electrodes formed using the same.

External electrodes of multilayer electronic components such as multilayer ceramic capacitors generally include a lower electrode layer formed on the surface of the multilayer body and a plating layer provided on the lower electrode layer. The lower electrode layer is often a sintered body layer formed by baking a conductive paste containing conductive powder such as Cu and Ni, glass powder, and an organic material. Here, because 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, one way to increase the size and capacity of a multilayer ceramic capacitor is to make the thickness of the external electrode as thin as possible and increase the volume of the stack that develops electrostatic capacity. For this purpose, it is necessary to thin the thickness of the lower electrode layer. On the other hand, if the lower electrode layer is thinned, there is a risk that moisture may easily infiltrate from the outside. Glass powder in the conductive paste is added to improve the sinterability of the conductive powder and to obtain a dense lower electrode layer that can suppress the intrusion of moisture from the outside.

As a component of the glass powder, a borosilicate glass composition containing B oxide and Si oxide as network-forming oxides and oxides of alkaline earth metal elements such as Ba, Ca, and Sr as modified oxides is often used. An example of a conductive paste containing glass powder using the above-described borosilicate glass composition is the conductive paste described in International Publication WO2014/175013 (Patent Document 1). The conductive paste disclosed in Patent Document 1 is baked into a laminate at 800°C to 900°C.

International Publication WO2014/175013

The conductive paste disclosed in Patent Document 1 is baked at 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 risk of cracks occurring. That is, in order to suppress the occurrence of cracks, it is necessary to lower the baking temperature of the conductive paste and reduce the degree of shrinkage of the lower electrode layer when cooling. On the other hand, if the baking temperature is lowered, the organic materials in the conductive paste remain without being sufficiently burned or decomposed, and there is a risk of inhibiting densification of the lower electrode layer. In addition, although densification is achieved, there is a risk that the adhesion between the laminate and the lower electrode layer may deteriorate.

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

The conductive paste according to the present disclosure includes conductive powder containing at least one element selected from Cu and Ni, 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 the mass spectrum obtained by mass analysis of the gas generated when the mixture of glass powder and C powder is heated to an elevated temperature has a gas generation peak with a mass number of 44 above 470°C and below 680°C.

The multilayer electronic component according to the present disclosure includes a laminate including a plurality of 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 laminate and electrically connected to the internal electrode layer. do. And the external electrode includes a lower electrode layer formed by baking the conductive paste according to the present disclosure.

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

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

The features of the present disclosure will be described with reference to the drawings. Meanwhile, in the embodiments of the multilayer electronic component shown below, identical or common parts are given the same reference numerals in the drawings, and their descriptions may not be repeated.

-Embodiment of conductive paste-

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

<Composition of conductive paste>

1 is a schematic diagram of the conductive paste 1. The conductive paste (1) includes conductive powder (2), glass powder (3), and organic material (4).

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

Additionally, at least a portion 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 Cu and Ni. Therefore, the sintering temperature of the conductive powder 2 having the above structure can be lowered.

Furthermore, at least part of the surface of the conductive powder 2 may be covered with an organic material layer. In this case, for example, effects such as steric hindrance repulsion or electrostatic repulsion are obtained due to the presence of the organic layer. As a result, even if the conductive powder 2 is fine, agglomeration of the conductive powder 2 in the conductive paste 1 can be suppressed.

And it is preferable that the average particle diameter of the conductive powder 2 is 1 μm or less. The average particle diameter of the conductive powder (2) is the equivalent circle converted diameter obtained from image analysis of the conductive powder (2) observed under a scanning electron microscope (hereinafter sometimes abbreviated as SEM). It was set to the median diameter. The median diameter of the equivalent circle conversion diameter is the particle size (D ₅₀ ) at which the integrated % is 50% in the distribution curve of the integrated % relative to the particle size. 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. Meanwhile, in Figure 1, the conductive powder 2 and the glass powder 3 are schematically depicted as spherical, but this is not the only shape of each powder. For example, the conductive powder 2 may contain flat conductive powder. The glass powder 3 may also contain glass powder of irregular shape.

The organic material 4 includes 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 organic materials for conductive pastes.

The glass powder 3 includes a borosilicate-based glass composition. A borosilicate-based glass composition is a glass composition that contains B oxide and Si oxide as network-forming oxides, and alkali metal element oxide and alkaline earth metal element oxide as modified oxides. 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 softening point of the measured object is measured using a thermogravimeter-differential thermal analyzer (hereinafter sometimes abbreviated as TG-DTA). Measurement conditions are described later.

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

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 analysis of the gas generated when the mixture of glass powder (3) and C powder is heated at an elevated temperature has a gas generation peak with a mass number of 44, that is, CO ₂ , above 470°C and below 680°C. has characteristics. In other words, the glass powder 3 softens and flows in the above temperature range and comes into contact with the residue of the organic material 4, thereby supplying O from the constituents of the glass fluid and promoting combustion of the residue of the organic material 4. there is.

On the other hand, the softening point of the glass composition is the temperature at which the viscosity η (Pa·s) of the glass composition becomes 6.65 or less in log η. If the temperature is close to the softening point, the glass composition softens and flows even if the temperature is below the softening point. Therefore, the softening point of the borosilicate-based glass composition contained in the glass powder 3 may be higher than the gas generation peak temperature of CO ₂ .

The above will be further explained using FIG. 2. FIG. 2 is a schematic diagram for explaining the assumed mechanism for acceleration of combustion of the organic material 4 by the glass powder 3. Figure 2(A) shows a state in which glass powder 3 and C component 5, which corresponds 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 is starting to soften and flow at this stage as well, the C component 5 may be surrounded by the glass powder 3 that is softening and flowing.

FIG. 2(B) shows the state in which the glass powder 3 is softened at a temperature slightly higher than the softening point to become the glass fluid 3f and is in contact with the C component 5. On the other hand, in FIG. 2(B), the 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 in a state in which they are partially in contact. In this state, O is supplied from the constituents of the glass fluid 3f.

FIG. 2(C) shows bubbles of gas containing CO ₂ in the glass fluid 3f due to combustion of the C component 5 receiving O at the temperature shown in FIG. 2(B) and at a higher temperature. (5g) indicates the created state. However, in this state, the viscosity of the glass fluid 3f has not decreased to the extent that the gas bubbles 5g burst, and the gas bubbles 5g remain within the glass fluid 3f.

Figure 2(D) shows that the viscosity of the glass fluid 3f is lowered at a temperature higher than the temperature shown in Figure 2(B), so that the gas bubbles 5g burst and CO is released from the glass fluid 3f. It indicates the state in which the gas containing ₂ is missing. As a result, the gas generation peak of CO ₂ is detected in mass analysis of the gas generated when the object to be measured is heated.

Meanwhile, as described above, although the above mechanism is a reasonable estimate, there is a possibility that other factors are involved. In other words, it should be noted that the conditions of the conductive paste in the present disclosure are not necessarily explained only by the above mechanism.

Mass analysis of the gas generated when the object to be measured is heated is performed using a thermogravimetry-mass spectrometer (hereinafter sometimes abbreviated as TG-MS). Measurement conditions are 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, necking between the conductive powders 2 is not inhibited by the residual organic component derived from the organic material 4, and sintering of the conductive powders 2 is promoted. Therefore, densification of the lower electrode layer is promoted, and deterioration of bonding between the laminate and the lower electrode layer is suppressed.

The borosilicate-based glass composition contained in the glass powder 3 preferably contains 36 mol% to 68 mol% of at least one type of first element (M1) that becomes a modified oxide among the constituent elements excluding oxygen. Here, the modified oxide in the present disclosure is a concept referring to oxides other than network-forming oxides (Si oxide and B oxide) in the glass composition. That is, the modified oxide in the present disclosure also includes Al oxide and the like, which are so-called intermediate oxides in glass compositions. 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.

Additionally, the first element (M1) preferably contains at least one element selected from Li, Na, and K. In this case, the softening point of the borosilicate-based glass composition can be adjusted more easily.

The borosilicate-based glass composition contained in the glass powder (3) has a standard free energy of formation (ΔG _M °) of the oxide above the softening point of the first element (M1) greater than the standard free energy of formation (ΔG _C °) of CO ₂ It is preferable to contain 1.5 mol% or more and 6.5 mol% or less of at least one type of second element (M2) that becomes an oxygen supply oxide. Meanwhile, this ratio is for constituent elements excluding oxygen.

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

The above will be further explained using FIG. 3. Figure 3 is a graph showing the relationship between the standard free energy of formation of oxides of Cu, Ni, Co and C and temperature, the so-called Elling sensitivity. In the area below the line showing the relationship between the standard free energy of formation (ΔG°) of the oxide and temperature, the element alone is stable, and in the area above it, the oxide is stable.

In other words, Eling sensitivity expresses the stability of oxides of various elements in relation to the equilibrium oxygen partial pressure. From the Elling sensitivity, it is possible to know which reducing agent should be used at what temperature to reduce the oxide of a certain element, and whether the metal is oxidized under a certain oxygen partial pressure.

Looking at the line related to the oxidation of C (solid line) and the line related to the oxidation of Cu (broken line) shown in FIG. 3, it is above the softening point of the glass powder 3, that is, 455°C or higher, and the line related to the oxidation of C is The line is located in an area below the line related to Cu oxidation. Therefore, in the region between the line related to the oxidation of Cu and the line related to the oxidation of C, Cu alone is stable, and C is stable as 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 above region, and the oxygen necessary to burn C is released. can be supplied.

Figure 3 also shows a line relating to the oxidation of Co (dash-dotted line) and a line relating to the oxidation of Ni (dash-dotted line). As above, these are also above the softening point of the glass powder 3, and the line related to the oxidation of C is located in a lower region than the line related to the oxidation of Co and the line related to the oxidation of Ni. Therefore, even when Co and Ni are included as second elements (M2) among the first elements (M1) that are the modified oxides of the borosilicate-based glass composition, the same effect can be exerted.

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

For example, when at least a portion of the surface of the conductive powder 2 is covered with an organic material layer, the conductive paste 1 before baking has more moisture content than when the conductive powder 2 is not covered with an organic material layer. It contains organic materials. That is, the organic material in the conductive paste remains without being sufficiently burned or decomposed, and tends to inhibit densification of the lower electrode layer.

However, when the second element (M2) is included in the first element (M1) as described above, 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. there is. This effect becomes particularly noticeable when the average particle diameter of the conductive powder 2, from which CO ₂ is difficult to escape, is 1 μm or less during baking of the conductive paste 1.

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, the softening point of the borosilicate-based glass composition can be adjusted more easily.

-Embodiment of multilayer electronic components-

A multilayer ceramic capacitor 100, which represents an embodiment of a multilayer electronic component according to the present disclosure, will be described using FIGS. 4 and 5.

Figure 4 is a cross-sectional view of the multilayer ceramic condenser 100. The multilayer ceramic condenser 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 is disposed 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. . The inner layer portion is arranged in a region sandwiched between the two outer layer portions.

The plurality of internal electrode layers 12 includes 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 in the stacking direction, a first side and a second side facing in a width direction perpendicular to the stacking direction, and a longitudinal direction perpendicular to the stacking direction and width direction. It has a first end face (13a) and a second end face (13b) facing each other.

The dielectric layer 11 has a plurality of crystal grains containing, for example, a BaTiO ₃ -based perovskite type compound. Examples of the dielectric material include those in which a portion 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, BaTiO ₃ -based perovskite-type compounds include BaTiO ₃ and those in which at least one of Ba ²⁺ and Ti ⁴⁺ of BaTiO ₃ is replaced by other ions such as Ca ²⁺ and Zr ^4+. there is.

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 portion from the counter electrode portion to the first end surface 13a of the laminate 10. It includes a lead-out electrode portion. The second internal electrode layer 12b includes a counter electrode portion facing the first internal electrode layer 12a with the dielectric layer 11 interposed therebetween, and a portion from the counter electrode portion to the second end surface 13b of the laminate 10. It includes a lead-out electrode portion.

One condenser is formed by opposing each other with the first internal electrode layer 12a and the second internal electrode layer 12b interposed between the dielectric layers 11. The multilayer ceramic capacitor 100 can be said to have a plurality of capacitors connected in parallel through first external electrodes 14a and second external electrodes 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, and Pd, or an alloy containing the metal may be used. The internal electrode layer 12 may further include dielectric particles called co-materials (not shown), as will be described later. The co-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 during firing of the laminate 10, and a portion of it remains in the internal electrode layer 12. There are cases where it happens. The co-material is added to make 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.

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 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 second main surface. 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 laminate 10 to be electrically connected to the second internal electrode layer 12b, and extends from the second end surface 13b to the first and second main surfaces. 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. Likewise, 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.

FIG. 5 is a cross-sectional view for explaining the 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 , subsequent description is 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 contains a metal sintered body in which the conductive powder 2 included in the conductive paste 1 is sintered. The glass region 16a ₁ contains glass components derived from the glass powder 3 . On the other hand, the sintered body layer may be formed in multiple layers of 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 above metals can be used. there is. The plating layer may be formed in multiple layers from different components. Preferably, it is two layers: a Ni plating layer and a Sn plating layer.

The Ni plating layer is disposed on the lower electrode layer and can prevent the lower electrode layer from being eroded by solder when mounting a multilayer electronic component. The Sn plating layer is disposed on the Ni plating layer. Since the Sn plating layer has good wettability with solder containing Sn, mountability can be improved when mounting multilayer electronic components. Meanwhile, 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 the conductive paste 1, where densification is promoted and deterioration of adhesion to the laminate is suppressed.

-Experimental example-

The conductive paste according to the present disclosure is explained in more detail based on the following experimental examples. These experimental examples are also intended to provide 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 from Sample No. 1 to Sample No. 20 were produced, and evaluation of softening point by TG-DTA and evaluation of the generation behavior of CO ₂ gas from a mixture of glass powder and C powder were conducted by TG-MS. .

In addition, a conductive paste was produced using glass powder of Sample No. 1 to Sample No. 20, Cu powder with an average particle diameter of 0.5 μm, and an organic material, and the lower electrode layer of the external electrode was formed using them, as shown in FIG. 4. A ceramic condenser was manufactured. On the other hand, the dielectric layer in the multilayer ceramic capacitor laminate 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 adhesion between the lower electrode layer of the external electrode and the laminate and the density of the lower electrode layer were evaluated.

The softening point evaluation of the glass powder of Sample No. 1 to Sample No. 20 by TG-DTA was conducted under the conditions shown in Table 1.

Evaluation of the generation behavior of CO ₂ gas in the mixture of glass powder and C powder of Sample No. 1 to Sample No. 20 by TG-MS was conducted under the conditions shown in Table 2.

The evaluation of the bonding properties of 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 No. 1 to Sample No. 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 No. 1 to Sample No. 20 was conducted under the conditions shown in Table 4.

The results of the softening point evaluation conducted as described above, the evaluation results of the generation behavior of CO ₂ gas, the evaluation results of the adhesion between the lower electrode layer and the laminate, and the denseness evaluation results of the lower electrode layer are summarized in Table 5.

In Table 5, sample numbers marked with * are samples that deviate from the conditions defining the conductive paste according to the present disclosure.

As described above, for example, in the borosilicate-based glass composition of Sample No. 2, B oxide and Si oxide are network-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 expressed in mol% as the total ratio of each element of Ba, Ca, Al, Mn, Cu, and Ti among the constituent elements of the borosilicate glass composition excluding O. As shown in Table 5, it was confirmed that each sample that met the conditions defining the conductive paste according to the present disclosure had good adhesion between the lower electrode layer and the laminate and good density of the lower electrode layer.

The embodiments disclosed in this specification are illustrative, 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 all changes within the meaning and scope equivalent to the claims are included. Additionally, 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 regarding the number of dielectric layers and internal electrode layers constituting the laminate, the materials of the dielectric layers and internal electrode layers, etc. In addition, a multilayer ceramic capacitor is exemplified as a multilayer electronic component, but the invention according to the present disclosure is not limited thereto and can also be applied to condenser elements formed inside a multilayer substrate.

Moreover, the number and location 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: glassy fluid
4: Organic materials
5: C component
5g: bubbles of gas
100: Multilayer ceramic condenser
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 : first plating layer
14b: second external electrode
14b ₁ : second lower electrode layer
14b ₂ : second plating layer
15a ₁ : conductive area
16a ₁ : glass area
M1: first element
M2: second element
ΔG°: standard free energy of formation of oxide
ΔG _M °: standard free energy of formation of oxides of secondary elements
ΔG _C °: Standard free energy of formation of _CO2

Claims (7)

Containing 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 with a softening point of 455°C or more and 650°C or less, and a mass spectrum obtained by mass analysis of the gas generated when the mixture of the glass powder and C powder is heated to an elevated temperature. ) has a gas generation peak with a mass number of 44 above 470℃ and below 680℃,
The borosilicate-based glass composition contains 36 mol% to 68 mol% of at least one type of first element that becomes a modified oxide among the constituent elements excluding oxygen,
The first element includes at least one element selected from Li, Na, and K,
The borosilicate-based glass composition contains at least 1.5 mol% or more of 6.5 mol% of at least one type of second element that becomes an oxygen-supplying oxide whose standard free energy of formation of the oxide above the softening point of the first element is greater than the standard free energy of formation of CO ₂ Contains % or less,
A conductive paste wherein the second element contains Ni. delete delete According to paragraph 1,
A conductive paste wherein at least a portion of the surface of the conductive powder is covered with a metal layer containing at least one element selected from Ag, Sn, and Al. delete According to paragraph 1,
A conductive paste wherein the average particle diameter of the conductive powder is 1 μm or less. A laminate including a plurality of 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 laminate and electrically connected to the internal electrode layer,
The external electrode is a multilayer electronic component including a lower electrode layer formed by baking the conductive paste according to claim 1.