JP7092103B2 - Conductive paste and laminated electronic components - Google Patents

Description

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

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

For example, as one means for promoting the miniaturization and large capacity of the multilayer ceramic capacitor, the thickness of the external electrode may be made as thin as possible, and the volume of the laminate expressing the capacitance may be increased. For that purpose, it is necessary to reduce the thickness of the base electrode layer. On the other hand, if the base electrode layer is made thin, there is a possibility that moisture easily infiltrates from the outside. The glass powder in the conductive paste is added to improve the sinterability of the conductive powder and to obtain a dense base electrode layer capable of suppressing the infiltration of water from the outside.

As a component of the glass powder, a borosilicate glass composition containing a network-forming oxide containing a B oxide and a Si oxide and an alkaline earth metal element oxide such as Ba, Ca and Sr as a modified oxide is used. Often. As an example of the conductive paste containing the glass powder using the borosilicate glass composition as described above, the conductive paste described in International Publication No. 2014/175013 (Patent Document 1) can be mentioned. The conductive paste disclosed in Patent Document 1 is baked onto a laminate at 800 ° C to 900 ° C.

International Publication No. 2014/175013

The conductive paste disclosed in Patent Document 1 is baked at a high temperature as described above. Therefore, when the base 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 laminated body, and 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 reduce the degree of shrinkage when the base electrode layer is cooled. On the other hand, when the baking temperature is lowered, the organic material in the conductive paste remains without being sufficiently burned or decomposed, which may hinder the densification of the base electrode layer. In addition, although it is densified, there is a risk that the bondability between the laminated body and the base electrode layer will deteriorate.

The object of this disclosure is an external electrode including a conductive paste capable of obtaining a base electrode layer which is dense at a low baking temperature and has high bondability with a laminate, and a base electrode layer formed by using the conductive paste. It is to provide a laminated electronic component provided.

The conductive paste according to this disclosure includes a conductive powder containing at least one element selected from Cu and Ni, a glass powder, and an organic material. The glass powder contains a borosilicate glass composition having a softening point of 455 ° C. or higher and 650 ° C. or lower. The mass spectrum obtained by mass spectrometry of the gas generated when the mixture of the glass powder and the C powder is heated and heated has a gas generation peak having a mass number of 44 at 470 ° C. or higher and 680 ° C. or lower.

The laminated electronic component according to this disclosure is formed in a laminated body including a plurality of laminated dielectric layers and a plurality of internal electrode layers at different positions on the outer surface of the laminated body, and is formed on the internal electrode layer. It has a plurality of external electrodes that are electrically connected. The external electrode includes a base electrode layer formed by baking the conductive paste according to the present disclosure.

The conductive paste according to this disclosure can obtain a base electrode layer that is dense at a low baking temperature and has high bondability with a laminate. Further, the laminated electronic component according to the present disclosure may include an external electrode including the above-mentioned base electrode layer formed by baking the conductive paste according to the present disclosure.

It is a schematic diagram of the conductive paste 1 which is the embodiment of the conductive paste which concerns on this disclosure. It is a schematic diagram for demonstrating the presumed mechanism about the promotion of combustion of the organic material 4 by a glass powder 3. 6 is a graph (Ellingham diagram) showing the relationship between the standard free energy of formation of oxides of Cu, Ni, Co and C and the temperature. It is sectional drawing of the laminated ceramic capacitor 100 which is embodiment of the laminated electronic component which concerns on this disclosure. It is sectional drawing for demonstrating the fine structure of the 1st base electrode layer 14a ₁ of the 1st external electrode 14a of a laminated ceramic capacitor 100.

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

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

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

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

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

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

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

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

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

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

The measurement of the softening point of the object to be measured is performed by a thermal weight / differential thermal analyzer (Thermogramter-Differential Thermal Analyzer: hereinafter abbreviated as TG-DTA). The 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 the softening point of the conventional borosilicate-based glass composition. Therefore, the base electrode layer formed by baking the conductive paste 1 provided with 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 laminated body is reduced, and the generation 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, which may hinder the densification of the base electrode layer.

Therefore, in the conductive paste 1 according to this 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 and heated has a mass number of 44, that is, a gas generation peak of CO ₂ at 470 ° C. or higher and 680 ° C. or lower. Has the characteristic of having. 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 constituent components of the glass fluid and promoting the combustion of the residue of the organic material 4. ing.

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 log η, and if the temperature is close to the softening point, it is not less than the temperature of the softening point. Even so, the glass composition is softened and fluidized. Therefore, the softening point of the borosilicate 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 described with reference to FIG. FIG. 2 is a schematic diagram for explaining a presumed mechanism for promoting combustion of the organic material 4 by the glass powder 3. FIG. 2A 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 has started the softening flow even at this stage, the C component 5 may be in a state of being wrapped by the glass powder 3 which is softening and flowing.

FIG. 2B shows a state in which the glass powder 3 softens to become a glass fluid 3f at a temperature slightly higher than the softening point and is in contact with the C component 5. Although FIG. 2B shows a state in which the C component 5 is surrounded by the glass fluid 3f, the C component 5 and the glass fluid 3f may be in partial contact with each other. .. In this state, O is supplied from the constituents of the glass fluid 3f.

FIG. 2C shows a gas containing CO ₂ in the glass fluid 3f due to the combustion of the C component 5 that received O at the temperature shown in FIG. 2B and at a temperature higher than that. Shows the state in which 5 g of bubbles are produced. However, in this state, the viscosity of the glass fluid 3f is not lowered to the extent that the gas bubbles 5g burst, and the gas bubbles 5g remain in the glass fluid 3f.

In FIG. 2D, the viscosity of the glass fluid 3f further decreases at a temperature higher than the temperature in the state shown in FIG. 2B, so that 5 g of gas bubbles burst from the glass fluid 3f. Indicates a state in which gas containing CO ₂ has escaped. 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 and heated.

As mentioned above, although the above mechanism is reasonably estimated, other factors may be involved. That is, it should be noted that the conditions of the conductive paste in this disclosure do not necessarily require explanation by the above mechanism alone.

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

Since the conductive paste 1 according to the present disclosure includes the glass powder 3 having the above-mentioned 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 hindered by the residual organic component derived from the organic material 4, and the sintering of the conductive powder 2 is promoted. Therefore, the densification of the base electrode layer is promoted, and the deterioration of the bondability between the laminated body and the base electrode layer is suppressed.

The borosilicate-based glass composition contained in the glass powder 3 preferably contains at least one first element M1 as a modified oxide among the constituent elements excluding oxygen in an amount of 36 mol% or more and 68 mol% or less. Here, the modified oxide in this disclosure is a concept that refers to an oxide other than the network-forming oxide (Si oxide and B oxide) in the glass composition. That is, the modified oxide in this disclosure also includes an Al oxide or the like, which is a so-called intermediate oxide in the glass composition. In this case, the softening point of the borosilicate glass composition can be easily adjusted to 455 ° C. or higher and 650 ° C. or lower.

Further, 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 glass composition can be adjusted more easily.

In the borosilicate-based glass composition contained in the glass powder 3, the standard formation free energy ΔG _M ° of the oxide at the softening point or higher of the first element M1 is larger than the standard formation free energy ΔG _C ° of CO ₂ . It is preferable to contain at least one kind of second element M2 serving as an oxygen supply oxide in an amount of 1.5 mol% or more and 6.5 mol% or less. It should be noted that this ratio is for the constituent elements excluding oxygen.

That is, in a state where the above-mentioned 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 added from the second element M2 in the glass fluid 3f. Be supplied. In this case, in the mass spectrum of the mixture of the glass powder 3 and the C powder by TG-MS, the gas generation peak of CO ₂ can be easily generated at 470 ° C. or higher and 680 ° C. or lower.

The above will be further described with reference to FIG. FIG. 3 is a graph showing the relationship between the standard free energy of formation of oxides of Cu, Ni, Co and C and temperature, a so-called Ellingham diagram. Elemental substances are stable in the region below the line representing the relationship between the standard free energy of oxide ΔG ° and temperature, and the oxide is stable in the region above.

That is, the Ellingham diagram shows the stability of oxides of various elements in relation to the partial pressure of equilibrium oxygen. From the Ellingham diagram, know what reducing agent should act at what temperature to reduce the oxide of an element, and whether the metal oxidizes under a certain oxygen partial pressure. Can be done.

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, the oxidation of C occurs at the softening point or higher of the glass powder 3, that is, at 455 ° C. or higher. The relevant line is located in the 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 contained as the second element M2 in the first element M1, the Cu oxide of the borosilicate glass composition is reduced under the temperature and oxygen partial pressure in the above region, and C. Can supply the oxygen needed to burn.

In FIG. 3, a line relating to the oxidation of Co (dashed line) and a line relating to the oxidation of Ni (dashed line) are also shown. Similar to the above, these are also located in the region above the softening point of the glass powder 3 and below the line related to the oxidation of C and the line related to the oxidation of Ni. Therefore, the same effect can be obtained when Co and Ni are contained as the second element M2 in the first element M1 which is the modified oxide of the borosilicate glass composition.

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 effectively burned even if the baking temperature of the conductive paste 1 is low. can. In other words, in the above case, the gas generation peak of CO ₂ can be easily generated at 470 ° C. or higher and 680 ° C. or lower in the mass spectrum of the mixture of the glass powder 3 and the C powder by TG-MS.

For example, when at least a part of the surface of the conductive powder 2 is covered with the organic layer, the conductive paste 1 before baking is more than the case where the conductive powder 2 is not covered with the organic layer. Will contain organic materials. That is, the organic material in the conductive paste remains without being sufficiently burned or decomposed, and it becomes easy to hinder the densification of the base electrode layer.

However, when the second element M2 is contained in the first element M1 as described above, the organic material 4 in the conductive paste 1 can be effectively used even if the baking temperature of the conductive paste 1 is low. Can be burned. This effect is particularly remarkable when the average particle size of the conductive powder 2 in 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, the softening point of the borosilicate glass composition can be adjusted more easily.

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

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

The plurality of internal electrode layers 12 have a first internal electrode layer 12a and a second internal electrode layer 12b. The laminate 10 has a first main surface and a second main surface facing the stacking direction, a first side surface and a second side surface facing the width direction orthogonal to the stacking direction, and the stacking direction and the width direction. It has a first end face 13a and a second end face 13b 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-type compound. Examples of the above-mentioned dielectric material include those in which a part of Ba ²⁺ in the crystal lattice of a BaTiO ₃ -based perovskite-type compound is replaced by Re ³⁺ , which is an ion of a rare earth element. Further, as the BaTIO ₃ type perovskite type compound, BaTIO ₃ and at least one of Ba2 ⁺ and Ti ⁴⁺ of BaTIO ₃ are substituted with other ions such as Ca ²⁺ and Zr ⁴⁺ . Can be mentioned.

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

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

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

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

The first external electrode 14a has a first base electrode layer 14a ₁ and a first plating layer 14a ₂ arranged on the first base electrode layer 14a ₁ . The first base electrode layer 14a ₁ 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 base electrode layer 14b ₁ and a second plating layer 14b ₂ arranged on the second base electrode layer 14b ₁ . The second base electrode layer 14b ₁ 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 fine structure of the first base electrode layer 14a ₁ . Since the second base electrode layer 14b ₁ has the same structure as the first base electrode layer 14a ₁ , the following description will be omitted. The sintered body layer included in the first base electrode layer 14a ₁ includes a conductor region 15a ₁ and a glass region 16a ₁ . The conductor region 15a ₁ contains a metal sintered body obtained by sintering the conductive powder 2 included in the conductive paste 1. The glass region 16a ₁ contains a glass component derived from the glass powder 3. The sintered body layer may be formed of a plurality of layers with different components.

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

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

The laminated ceramic capacitor 100 according to the present disclosure may include an external electrode formed by baking the conductive paste 1 and including a base electrode layer in which densification is promoted and deterioration of bondability with the laminate is suppressed. can.

-Experimental example-
The conductive paste according to this disclosure will be described more specifically based on the following experimental examples. These experimental examples are also intended to provide a basis for defining the conditions of the conductive paste according to this disclosure, or more preferable conditions. In the experimental example, the glass powder of sample No. 1 to sample No. 20 was prepared, the softening point was evaluated by TG-DTA, and the generation behavior of CO2 gas in the mixture of glass powder and C powder was evaluated by TG-MS. I was broken.

Further, a conductive paste was prepared using the glass powders of sample numbers 1 to 20 and Cu powder having an average particle size of 0.5 μm and an organic material, and the base electrode layer of the external electrode was formed by using them. , A monolithic ceramic capacitor as shown in FIG. 4 was manufactured. The dielectric layer in the laminated body of the laminated ceramic capacitor is formed of a dielectric material containing a BaTiO ₃ -based perovskite-type compound, and the internal electrode layer is formed of Ni. Using these multilayer ceramic capacitors, the bondability between the base electrode layer of the external electrode and the laminated body was evaluated, and the denseness of the base electrode layer was evaluated.

The evaluation of the softening points of the glass powders of Sample Nos. 1 to 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 the C powder of sample numbers 1 to 20 by TG-MS was performed under the conditions shown in Table 2.

Table 3 shows the evaluation of the bondability between the base electrode layer and the laminate in the laminated ceramic capacitor in which the base electrode layer of the external electrode was formed by baking the conductive paste containing the glass powder of sample numbers 1 to 20. It was done according to the conditions.

The evaluation of the denseness of the base electrode layer in the laminated ceramic capacitor in which the base 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 based on the conditions shown in Table 4. It was conducted.

The table below shows the evaluation results of the softening points, the evaluation results of the generation behavior of CO ₂ gas, the evaluation results of the bondability between the base electrode layer and the laminate, and the evaluation results of the denseness of the base electrode layer. It is shown collectively in 5.

Sample numbers marked with * in Table 5 are samples that do not meet the conditions that specify the conductive paste according to this disclosure.

As described above, for example, in the borosilicate glass composition of Sample No. 2, the B oxide and the Si oxide are network-forming oxides, and the Ba, Ca, Al, Mn, Cu and Ti oxides are the network-forming oxides. Considered a modified oxide. That is, the ratio of the first element M1 is such that the total ratio of each element of Ba, Ca, Al, Mn, Cu and Ti among the constituent elements of the above borosilicate glass composition excluding O is mol%. It is represented. As shown in Table 5, it was confirmed that the bondability between the base electrode layer and the laminate and the denseness of the base electrode layer were good in each sample satisfying the conditions defining the conductive paste according to this disclosure. Was done.

The embodiments disclosed in this specification are exemplary, and the invention according to this disclosure is not limited to the above-described embodiment. That is, the scope of the invention according to this disclosure is indicated by the scope of claims, and is intended to include all modifications within the meaning and scope equivalent to the scope of claims. Further, various applications and modifications can be added 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 layers of the dielectric layer and the internal electrode layer constituting the laminated body, the materials of the dielectric layer and the internal electrode layer, and the like. Further, although a laminated ceramic capacitor has been exemplified as a laminated electronic component, the invention according to this disclosure is not limited to this, and can be applied to a capacitor element formed inside a multilayer substrate and the like.

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

1 Conductive paste 2 Conductive powder 3 Glass powder 3f Glass fluid 4 Organic material 5 C component 5g Gas foam 100 Multilayer ceramic capacitor 10 Laminated body 11 Dielectric layer 12 Internal electrode layer 13a First end face 13b Second end face 14a First external electrode 14a ₁ First base electrode layer 14a ₂ First plating layer 14b Second external electrode 14b ₁ Second base electrode layer 14b ₂ Second plating layer 15a ₁ Conductive region 16a ₁ Glass Region M1 First element M2 Second element ΔG ° Standard formation free energy of oxide ΔG _M ° Standard formation free energy of oxide of second element ΔG _C ° Standard formation free energy of CO ₂

Claims (8)

It comprises a conductive powder containing at least one element selected from Cu and Ni, a glass powder, and an organic material.
The glass powder contains a borosilicate-based glass composition having a softening point of 455 ° C. or higher and 650 ° C. or lower, and is a mass obtained by mass spectrometry of a gas generated during heating and heating of a mixture of the glass powder and C powder. The spectrum has a gas generation peak having a mass number of 44 at 470 ° C or higher and 680 ° C or lower.
A conductive paste in which the surface of at least a part of the conductive powder is coated with a metal layer containing at least one element selected from Ag, Sn and Al . It comprises a conductive powder containing at least one element selected from Cu and Ni, a glass powder, and an organic material.
The glass powder contains a borosilicate-based glass composition having a softening point of 455 ° C. or higher and 650 ° C. or lower, and is a mass obtained by mass spectrometry of a gas generated during heating and heating of a mixture of the glass powder and C powder. The spectrum has a gas generation peak having a mass number of 44 at 470 ° C or higher and 680 ° C or lower.
A conductive paste in which at least a part of the surface of the conductive powder is coated with an organic substance layer. It comprises a conductive powder containing at least one element selected from Cu and Ni, a glass powder, and an organic material.
The glass powder contains a borosilicate-based glass composition having a softening point of 455 ° C. or higher and 650 ° C. or lower, and is a mass obtained by mass spectrometry of a gas generated during heating and heating of a mixture of the glass powder and C powder. The spectrum has a gas generation peak having a mass number of 44 at 470 ° C or higher and 680 ° C or lower.
A conductive paste having an average particle size of 1 μm or less. One of claims 1 to 3, wherein the borosilicate glass composition contains at least one first element as a modified oxide among the constituent elements excluding oxygen in an amount of 36 mol% or more and 68 mol% or less. The conductive paste described in. The conductive paste according to claim 4, wherein the first element contains at least one element selected from Li, Na and K. In the borosilicate glass composition, among the first elements, the standard free energy for forming an oxide at the softening point or higher is CO. ₂ The conductive paste according to any one of claims 4 or 5, which contains at least 1.5 mol% or more and 6.5 mol% or less of the second element which is an oxygen supply oxide larger than the standard free energy of formation. .. The conductive paste according to claim 6, wherein the second element contains at least one element selected from Cu, Co and Ni. A plurality of laminated bodies including a plurality of laminated dielectric layers and a plurality of internal electrode layers, and a plurality of laminated bodies formed at different positions on the outer surface of the laminated body and electrically connected to the internal electrode layers. Equipped with external electrodes,
The external electrode is a laminated electronic component including a base electrode layer formed by baking the conductive paste according to any one of claims 1 to 7.

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