The present invention relates to multilayer ceramic electronic components.
In the related art, multilayer ceramic capacitors as multilayer ceramic electronic components have been known. In general, multilayer ceramic capacitors each include a multilayer body including a plurality of dielectric layers and a plurality of internal electrode layers alternately laminated therein, and external electrodes provided on both end surfaces of the multilayer body. For example, Japanese Unexamined Patent Application Publication No. 2003-243249 discloses a multilayer ceramic capacitor having the above-described configuration and external electrodes, each including a base electrode layer provided by firing.
Here, in the multilayer ceramic capacitor described in Japanese Unexamined Patent Application Publication No. 2003-243249, the external electrodes (external electrode layers) are electrically connected to the internal electrodes (internal electrode layers) and prevent moisture from entering the end surfaces of the multilayer body from the outside. On the other hand, when a force is applied to the external electrodes, cracks may occur in the multilayer bodies of the multilayer ceramic capacitors.
Example embodiments of the present invention provide multilayer ceramic electronic components, each having high crack resistance.
An example embodiments of the present invention provides a multilayer ceramic electronic component that include a multilayer body including a plurality of ceramic layers and a plurality of internal conductive layers which are alternately laminated therein in a lamination direction, a first main surface and a second main surface which are opposed to each other in the lamination direction, a first end surface and a second end surface which are opposed to each other in a length direction perpendicular or substantially perpendicular to the lamination direction, and a first lateral surface and a second lateral surface which are opposed to each other in a width direction perpendicular or substantially perpendicular to the lamination direction and the length direction, and a pair of external electrodes on both ends of the multilayer body in the length direction and spaced apart from each other, in which the plurality of internal conductive layers include first internal conductive layers each extending toward and exposed at the first end surface, and second internal conductive layers each extending toward and exposed at the second end surface, the pair of external electrodes include a first external electrode including a first base electrode layer connected to the first internal conductive layer, and a second external electrode including a second base electrode layer connected to the second internal conductive layer, the first base electrode layer and the second base electrode layer each include a metal portion and a plurality of non-metal portions existing in the metal portion, and, in a cross sectional view perpendicular or substantially perpendicular to the width direction, an average area of a plurality of non-metal portions in a first population of a plurality of non-metal portions, each having a circularity of about 0.4 or less, is about 10 μm2 or more, and, in a cross sectional view perpendicular or substantially perpendicular to the width direction, a proportion of the plurality of non-metal portions in each of the first base electrode layer and the second base electrode layer is about 8.2% or more.
According to example embodiments of the present invention, it is possible to provide multilayer ceramic electronic components, each having high crack resistance.
The above other and elements, features, steps, characteristics and advantages of the present invention will become more apparent from the following detailed description of the example embodiments with reference to the attached drawings.
Example embodiments of the present invention will be described in detail below with reference to the drawings.
A multilayer ceramic capacitor 1 defining and functioning as a multilayer ceramic electronic component according to an example embodiment of the present invention of the present invention will be described.
As shown in
In
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The dimensions of the multilayer body 10 are not particularly limited. However, when the dimension in the length direction L of the multilayer body 10 is defined as L dimension, the L dimension is preferably about 0.2 mm or more and about 6 mm or less, for example. When the dimension of the multilayer body 10 in the lamination direction T is defined as T dimension, the T dimension is preferably about 0.05 mm or more and about 5 mm or less, for example. When the dimension of the multilayer body 10 in the width direction W is defined as W dimension, the dimension W is preferably about 0.1 mm or more and about 5 mm or less, for example.
As shown in
The inner layer portion 11 includes a plurality of dielectric layers 20 defining and functioning as a plurality of ceramic layers and a plurality of internal electrode layers 30 defining and functioning as a plurality of internal conductive layers which are alternately laminated in the lamination direction T. The inner layer portion 11 includes, in the lamination direction T, from the internal electrode layer 30 located closest to the first main surface TS1 until the internal electrode layer 30 located closest to the second main surface TS2. In the inner layer portion 11, a plurality of internal electrode layers 30 are opposed to each other with the dielectric layer 20 interposed therebetween. The inner layer portion 11 generates a capacitance and substantially defines and functions as a capacitor.
The plurality of dielectric layers 20 are each made of a dielectric material. The dielectric material may preferably be a dielectric ceramic including a component such as, for example, BaTiO3, CaTio3, SrTiO3, or CaZrO3. Furthermore, the dielectric material may be obtained by adding a secondary component such as, for example, a Mn compound, an Fe compound, a Cr compound, a Co compound, or a Ni compound to the main component. The dielectric material particularly preferably includes, for example, BaTiO3 as a main component.
The thicknesses of the dielectric layers 20 are each preferably about 0.2 μm or more and about 10 μm or less, for example. The number of the dielectric layers 20 to be laminated (stacked) is preferably fifteen or more and 1200 or less, for example. The number of the dielectric layers 20 refers to the total number of dielectric layers 20 in the inner layer portion 11, and dielectric layers 20 in the first main surface-side outer layer portion 12 and the second main surface-side outer layer portion 13.
The plurality of internal electrode layers 30 includes a plurality of first internal electrode layers 31 defining and functioning as a plurality of first internal conductive layers and a plurality of second internal electrode layers 32 defining and functioning as a plurality of second internal conductive layers. The first internal electrode layers 31 and the second internal electrode layers 32 are alternately provided in the lamination direction T with the dielectric layers 20 interposed therebetween. The first internal electrode layers 31 each extend toward the first end surface LS1 and are each exposed at the first end surface LS1. The second internal electrode layers 32 each extend toward the second end surface LS2 and are each exposed at the second end surface LS2. In the following description, when it is not necessary to distinguish between the first internal electrode layer 31 and the second internal electrode layer 32, the first internal electrode layer 31 and the second internal electrode layer 32 may be collectively referred to as an internal electrode layer 30.
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In the present example embodiment, the first counter portion 31A and the second counter portion 32A are opposed to each other with the dielectric layer 20 interposed therebetween, such that a capacitance is generated, and the electrical properties of a capacitor are developed.
The shapes of the first counter portion 31A and the second counter portion 32A are not particularly limited, but are preferably rectangular or substantially rectangular. However, the corner portions of the rectangular shape may be rounded, or the corner portions of the rectangular shape may be provided obliquely. The shapes of the first extension portion 31B and the second extension portion 32B are not particularly limited, but are preferably rectangular or substantially rectangular. However, the corner portions of the rectangular shape may be rounded, or the corner portions of the rectangular shape may be provided obliquely.
The dimension of the first counter portion 31A in the width direction W and the dimension of the first extension portion 31B in the width direction W may be the same, or either one of them may be smaller. The dimension of the second counter portion 32A in the width direction W and the dimension of the second extension portion 32B in the width direction W may be the same, or either one of them may be narrower.
The first internal electrode layers 31 and the second internal electrode layers 32 are each made of an appropriate electrically conductive material including a metal such as, for example, Ni, Cu, Ag, Pd or Au, or an alloy including at least one of these metals. When using an alloy, the first internal electrode layers 31 and the second internal electrode layers 32 may be each made of, for example, an Ag—Pd alloy.
The thicknesses of the first internal electrode layers 31 and the second internal electrode layers 32 are each preferably, for example, about 0.2 μm or more and about 2.0 μm or less. The total number of the first internal electrode layers 31 and the second internal electrode layers 32 is preferably fifteen or more and 1000 or less.
As shown in
The multilayer body 10 includes a counter electrode portion 11E. The counter electrode portion 11E is a portion where the first counter portion 31A of the first internal electrode layer 31 and the second counter portion 32A of the second internal electrode layer 32 are opposed to each other. The counter electrode portion 11E defines and functions as a portion of the inner layer portion 11.
The multilayer body 10 includes lateral surface side-outer layer portions. The lateral surface side-outer layer portions include a first lateral surface side-outer layer portion WG1 and a second lateral surface side-outer layer portion WG2. The first lateral surface side-outer layer portion WG1 is a portion including the dielectric layer 20 located between the counter electrode portion 11E and the first lateral surface WS1. The second lateral surface side-outer layer portion WG2 is a portion including the dielectric layer 20 located between the counter electrode portion 11E and the second lateral surface WS2.
The multilayer body 10 includes end surface side-outer layer portions. The end surface side-outer layer portions include a first end surface side-outer layer portion LG1 and a second end surface side-outer layer portion LG2. The first end surface side-outer layer portion LG1 is a portion including the dielectric layer 20 and the first extension portion 31B located between the counter electrode portion 11E and the first end surface LS1. That is, the first end surface side-outer layer portion LG1 includes the portions of the plurality of dielectric layers 20 adjacent to the first end surface LS1 and the plurality of first extension portions 31B. The second end surface side-outer layer portion LG2 is a portion including the dielectric layer 20 and the second extension portion 32B located between the counter electrode portion 11E and the second end surface LS2. That is, the second end surface side-outer layer portion LG2 includes the portions of the plurality of dielectric layers 20 adjacent to the second end surface LS2 and the plurality of second extension portions 32B.
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In addition, the basic configurations of the first external electrode 40A and the second external electrode 40B are preferably the same or substantially the same. Furthermore, the first external electrode 40A and the second external electrode 40B have a shape that is substantially plane symmetrical with respect to the WT cross section at the center in the length direction L of the multilayer ceramic capacitor 1. Therefore, in the following description, when it is not necessary to distinguish between the first external electrode 40A and the second external electrode 40B, the first external electrode 40A and the second external electrode 40B may be collectively referred to as an external electrode 40.
The first external electrode 40A is provided on the first end surface LS1. The first external electrode 40A is in contact with the first extension portion 31B of each of the plurality of first internal electrode layers 31 exposed at the first end surface LS1. With such a configuration, the first external electrode 40A is electrically connected to the plurality of first internal electrode layers 31. The first external electrode 40A may be provided on a portion of the first main surface TS1 and a portion of the second main surface TS2, and also on a portion of the first lateral surface WS1 and a portion of the second lateral surface WS2. In the present example embodiment, the first external electrode 40A extends from the first end surface LS1 to a portion of the first main surface TS1 and to a portion of the second main surface TS2, and to a portion of the first lateral surface WS1 and to a portion of the second lateral surface WS2.
The second external electrode 40B is provided on the second end surface LS2. The second external electrode 40B is in contact with the second extension portion 32B of each of the plurality of second internal electrode layers 32 exposed at the second end surface LS2. With such a configuration, the second external electrode 40B is electrically connected to the plurality of second internal electrode layers 32. The second external electrodes 40B may be provided on a portion of the first main surface TS1 and a portion of the second main surface TS2, and also on a portion of the first lateral surface WS1 and a portion of the second lateral surface WS2. In the present example embodiment, the second external electrode 40B extends from the second end surface LS2 to a portion of the first main surface TS1 and to a portion of the second main surface TS2, and to a portion of the first lateral surface WS1 and a portion of the second lateral surface WS2.
As described above, in the multilayer body 10, the capacitance is generated by the first counter portions 31A of the first internal electrode layers 31 and the second counter portions 32A of the second internal electrode layers 32, which are opposed to each other with the dielectric layers 20 interposed therebetween. Therefore, characteristics of the capacitor are provided between the first external electrode 40A to which the first internal electrode layers 31 are connected and the second external electrode 40B to which the second internal electrode layers 32 are connected.
As shown in
The first base electrode layer 50A is provided on the first end surface LS1. The first base electrode layer 50A is connected to the first extension portion 31B of each of the plurality of first internal electrode layers 31 exposed at the first end surface LS1. In the present example embodiment, the first base electrode layer 50A extends from the first end surface LS1 to a portion of the first main surface TS1 and to a portion of the second main surface TS2, and to a portion of the first lateral surface WS1 and to a portion of the second lateral surface WS2.
The second base electrode layer 50B is provided on the second end surface LS2. The second base electrode layer 50B is in contact with the second extension portion 32B of each of the plurality of second internal electrode layers 32 exposed at the second end surface LS2. In the present example embodiment, the second base electrode layer 50B extends from the second end surface LS2 to a portion of the first main surface TS1 and to a portion of the second main surface TS2, and to a portion of the first lateral surface WS1 and to a portion of the second lateral surface WS2.
The first base electrode layer 50A and the second base electrode layer 50B of the present example embodiment are, for example, fired layers. It is preferable that the fired layers each include, for example, both a metal component, and either a glass component or a ceramic component, or both the glass component and the ceramic component. The metal component includes, for example, at least one selected from Cu, Ni, Ag, Pd, Ag—Pd alloys, Au, and the like. The glass component includes, for example, at least one selected from B, Si, Ba, Mg, Al, Li, and the like. As the ceramic component, the same or substantially same ceramic material as that of the dielectric layer 20 may be used, or a different ceramic material may be used. Ceramic components include, for example, at least one selected from BaTiO3, CaTio3, (Ba, Ca) TiO3, SrTiO3, CaZrO3, and the like.
Each of the fired layers is obtained by, for example, applying an electrically conductive paste including glass and metal to the multilayer body 10 and firing it. The fired layer can be obtained by simultaneously firing (co-firing) a multilayer chip before firing, which is a material of the multilayer body 10 having a plurality of internal electrodes and dielectric layers, and an electrically conductive paste applied to the multilayer chip. Alternatively, the multilayer chip may be fired to obtain the multilayer body 10, following which an electrically conductive paste may be applied to the multilayer body 10 and the resulting product may be fired. In a case of the above-described configuration, it is preferable that the fired layer is formed by, for example, baking a ceramic material added instead of the glass component. In such a case, it is particularly preferable to use, as the ceramic material to be added, the same or substantially the same kind of ceramic material as the dielectric layer 20. The fired layer may include a plurality of layers.
The thickness of the first base electrode layer 50A located on the first end surface LS1 in the length direction L is preferably, for example, about 10 μm or more and about 200 μm or less in the middle of the first base electrode layer 50A in the lamination direction T and the width direction W.
The thickness of the second base electrode layer 50B located on the second end surface LS2 in the length direction L is preferably, for example, about 10 μm or more and about 200 μm or less in the middle of the second base electrode layer 50B in the lamination direction T and the width direction W.
When providing the first base electrode layer 50A to at least one of portions of the first main surface TS1 and the second main surface TS2, the thickness in the lamination direction T of the first base electrode layer 50A provided at this portion is preferably about 3 μm or more and about 40 μm or less in the middle in the length direction L and the width direction W of the first base electrode layer 50A provided at this portion, for example.
When providing the first base electrode layer 50A to portions of at least one of the first lateral surface WS1 and the second lateral surface WS2, the thickness in the width direction W of the first base electrode layer 50A provided at this portion is preferably about 3 μm or more and about 40 μm or less in the middle in the length direction L and the lamination direction T of the first base electrode layer 50A provided at this portion, for example.
When providing the second base electrode layer 50B to portions of at least one of the first main surface TS1 and the second main surface TS2, the thickness in the lamination direction T of the second base electrode layer 50B provided at this portion is preferably about 3 μm or more and about 40 μm or less in the middle in the length direction L and the width direction W of the second base electrode layer 50B provided at this portion, for example.
When providing the second base electrode layer 50B to portions of at least one of the first lateral surface WS1 and the second lateral surface WS2, the thickness in the width direction W of the second base electrode layer 50B provided at this portion is preferably about 3 μm or more and about 40 μm or less in the middle in the length direction L and the lamination direction T of the second base electrode layer 50B provided at this portion, for example.
The first plated layer 60A covers the first base electrode layer 50A. The second plated layer 60B covers the second base electrode layer 50B. The first plated layer 60A and the second plated layer 60B may each include at least one material selected from, for example, Cu, Ni, Sn, Ag, Pd, a Ag—Pd alloy, Au, and the like. The first plated layer 60A and the second plated layer 60B may each include a plurality of layers. The first plated layer 60A and the second plated layer 60B each preferably include a two-layer structure including, for example, a Sn plated layer on a Ni plated layer.
The first plated layer 60A covers the first base electrode layer 50A. In the present example embodiment, the first plated layer 60A includes a first Ni plated layer 61A, and a first Sn plated layer 62A provided on the first Ni plated layer 61A.
The second plated layer 60B covers the second base electrode layer 50B. In the present example embodiment, the second plated layer 60B includes a second Ni plated layer 61B, and a second Sn plated layer 62B provided on the second Ni plated layer 61B.
The Ni plated layer prevents the first base electrode layer 50A and the second base electrode layer 50B from being eroded by solder when mounting the multilayer ceramic capacitor 1. Furthermore, the Sn plated layer improves the wettability of the solder when mounting the multilayer ceramic capacitor 1. This facilitates the mounting of the multilayer ceramic capacitor 1. The thickness of each of the first Ni plated layer 61A, the first Sn plated layer 62A, the second Ni plated layer 61B, and the second Sn plated layer 62B is preferably about 2 μm or more and about 10 μm or less, for example.
The external electrode 40 of the present example embodiment may include an electrically conductive resin layer including electrically conductive particles and a thermosetting resin, for example. The electrically conductive resin layer may cover the fired layer. When the electrically conductive resin layer covers the fired layer, the electrically conductive resin layer is provided between the fired layer and the plated layers (the first plated layer 60A and the second plated layer 60B). The electrically conductive resin layer may completely cover the fired layer or may partially cover the fired layer.
The electrically conductive resin layer including a thermosetting resin is more flexible than an electrically conductive layer made of, for example, a plated film or a fired product of an electrically conductive paste. Therefore, even when an impact caused by physical shock or thermal cycling is applied to the multilayer ceramic capacitor 1, the electrically conductive resin layer defines and functions as a buffer layer. Therefore, the electrically conductive resin layer reduces or prevents the occurrence of cracking in the multilayer ceramic capacitor 1.
Metals of the electrically conductive particles may preferably be, for example, Ag, Cu, Ni, Sn, Bi or alloys including them. The electrically conductive particle preferably includes Ag, for example. The electrically conductive particle is a metal powder of Ag, for example. Ag is suitable as an electrode material because of its lowest resistivity among metals. In addition, since Ag is a noble metal, it is not likely to be oxidized, and weatherability thereof is high. Therefore, the metal powder of Ag is suitable as the electrically conductive particle.
Furthermore, the electrically conductive particle may be a metal powder coated on the surface of the metal powder with Ag. When using these coated with Ag on the surface of the metal powder, the metal powder is preferably Cu, Ni, Sn, Bi, or an alloy powder thereof. In order to make the metal of the base material inexpensive while keeping the characteristics of Ag, it is preferable to use a metal powder coated with Ag.
Furthermore, the electrically conductive particle may be formed by, for example, subjecting Cu and Ni to an oxidation prevention treatment. Furthermore, for example, the electrically conductive particle may be a metal powder coated with Sn, Ni, and Cu on the surface of the metal powder. When using these coated with Sn, Ni, and Cu on the surface of the metal powder, the metal powder is, for example, preferably Ag, Cu, Ni, Sn, Bi, or an alloy powder thereof.
The shape of the electrically conductive particle is not particularly limited. For the electrically conductive particle, a spherical metal powder, a flat metal powder, or the like can be used. However, it is preferable to use a mixture of a spherical metal powder and a flat metal powder.
The electrically conductive particles included in the electrically conductive resin layer mainly play a role of ensuring the conductivity of the electrically conductive resin layer. Specifically, by a plurality of electrically conductive particles being in contact with each other, an energization path is provided inside the electrically conductive resin layer.
The resin of the electrically conductive resin layer may include, for example, at least one of a variety of known thermosetting resins such as epoxy resin, phenolic resin, urethane resin, silicone resin, polyimide resin, and the like. Among these, epoxy resin is excellent in heat resistance, moisture resistance, adhesion, etc., and thus is one of the more preferable resins. Furthermore, it is preferable that the resin of the electrically conductive resin layer includes a curing agent together with a thermosetting resin. When epoxy resin is used as a base resin, the curing agent of the epoxy resin may be various known compounds such as, for example, phenols, amines, acid anhydrides, imidazoles, active esters, and amide-imides.
The electrically conductive resin layer may include a plurality of layers. The thickest portion of the electrically conductive resin layer is, for example, preferably about 10 μm or more and about 150 μm or less.
The basic configuration of the multilayer ceramic capacitor 1 according to the example embodiment is described as above. When the dimension in the length direction of the multilayer ceramic capacitor 1 including the multilayer body 10 and the external electrodes 40 is defined as the L dimension, the L dimension is preferably about 0.2 mm or more and about 6 mm or less, for example. Furthermore, when the dimension in the lamination direction of the multilayer ceramic capacitor 1 is defined as the T dimension, the T dimension is preferably about 0.05 mm or more and about 5 mm or less, for example. Furthermore, when the dimension in the width direction of the multilayer ceramic capacitor 1 is defined as the W dimension, the W dimension is preferably about 0.1 mm or more and about 5 mm or less, for example.
The inventor of example embodiments of the present invention thoroughly conducted investigation, experiments, and simulations, and have discovered that it is preferable to set the base electrode layer in direct contact with the multilayer body, i.e., the non-metal portion included in the first base electrode layer 50A and the second base electrode layer 50B of the present example embodiment in an appropriate state in order to improve the crack resistance of the multilayer ceramic capacitors. This point will be described below.
The second base electrode layer 50B of the example embodiment also includes a cross-sectional structure the same as or similar to that of
As shown in
The metal portion 70 includes at least one metal component selected from, for example, Cu, Ni, Ag, Pd, an Ag—Pd alloy, Au, and the like included in the fired layer of the base electrode layer 50. The plurality of non-metal portions 80 are dispersed in the metal portion 70.
Although the plurality of non-metal portions 80 are mainly voids in the present example embodiment, all of the plurality of non-metal portions 80 may not be voids, and some of the plurality of non-metal portion 80 may include or partially include a glass component including Ba or Si, for example. Furthermore, all of the non-metal portion 80 may be made of a glass component including Ba or Si, for example. The plurality of non-metal portions 80 have different circularity and average area. The non-metal portions 80 relieve stress generated by a force applied to the external electrode.
In the base electrode layer 50 of the present example embodiment, for example, the average area of the plurality of non-metal portions 80 in the first population including the non-metal portions 80 having a circularity of about 0.4 or less is preferably about 10 μm2 or more in the LT cross-sectional view perpendicular or substantially perpendicular to the width direction W as shown in
Furthermore, in the base electrode layer 50 of the present example embodiment, for example, the proportion of the non-metal portions 80 is preferably about 8.2% or more in the LT cross-sectional view perpendicular or substantially perpendicular to the width direction W as shown in
In the multilayer ceramic capacitor 1 of the present example embodiment, non-metal portions 80 each having a low circularity among the non-metal portions 80 existing in the base electrode layer 50 have relatively large areas.
In the present example embodiment, for example, in the LT cross-sectional view of the base electrode layer 50, when the population of non-metal portions 80, each having a circularity of about 0.4 or less, is defined as a first population, the average area of the plurality of non-metal portions 80 of the first population is about 10 μm2 or more, and specifically, in the region shown in
In the present example embodiment, for example, the average area of the plurality of non-metal portions 80 of the first population is preferably about 10 μm2 or more and about 23 μm2 or less, and more preferably about 10.5 μm2 or more and about 23 μm2 or less. This further improves crack resistance.
In the multilayer ceramic capacitor 1 of the present example embodiment, the proportion of the non-metal portions 80 existing in the base electrode layer 50 in the LT cross-sectional view is, for example, preferably about 8.2% or more, and is more preferably about 8.2% or more and about 30% or less. More specifically, the proportion of the non-metal portions 80 existing in the base electrode layer 50 is preferably about 8.2% or more and about 25% or less, and more preferably about 11% or more and about 25% or less, for example. Even when the non-metal portion 80 is included in the base electrode layer 50 and the proportion of the non-metal portions 80 existing in the base electrode layer 50 falls within such a range, it is possible to achieve the advantageous effect of the present example embodiment, that is, the advantageous effect of improving crack resistance.
Next, an example of a method of measuring various parameters such as the circularity of the non-metal portion 80, the average area of the non-metal portions 80, and the proportion of the non-metal portions 80 existing in the base electrode layer 50 in the present example embodiment will be described.
First, the multilayer ceramic capacitor 1 is polished from the first lateral surface WS1 or the second lateral surface WS2 to a position about ½ of the width direction W. Thus, the LT cross section at the middle position in the width direction W of the multilayer ceramic capacitor 1 is exposed. Next, the LT cross section exposed by polishing is observed by SEM. Specifically, a portion including the base electrode layer 50 in the LT cross section is imaged as a reflected electron image. In the reflected electron image, the difference in resistance value is reflected as contrast, the metal portion 70 appears relatively white, and the non-metal portion 80 appears darker than the metal portion 70. In addition, the imaging magnification is set to 2000 times, and a portion of the base electrode layer 50 in the reflected electron image is set as an analysis target range.
A total of four reflected electron images of two locations of the first base electrode layer 50A and two locations of the second base electrode layer 50B are obtained. In
In the base electrode layer 50, the four regions corresponding to the respective reflected electron image acquisition positions R1, R2, R3, and R4 are each likely to have a singular point in structure, and have a high degree of influence on crack resistance. Therefore, the state of the base electrode layer 50 in these portions is important from the viewpoint of crack resistance.
The acquired reflected electron image is binarized by the image analysis software “WinROOF” (available from Mitani Corporation) to identify the metal portion 70 and a plurality of non-metal portions 80 existing in the metal portion 70. Using the binarized image, various parameters such as the area of each non-metal portion 80 existing in the base electrode layer 50 are calculated. Furthermore, the proportion of the non-metal portions 80 existing in the base electrode layer 50 is calculated.
The area of the non-metal portion 80 is calculated based on the binarized image obtained by binarizing the reflected electron image. When the area of the non-metal portion 80 is, for example, less than about 2.0 μm2, it may be noise instead of the non-metal portion 80. Therefore, for example, in order to exclude the influence of noise, the non-metal portions 80 of less than about 2.0 μm2 are excluded from the analysis target.
For each non-metal portion 80, the circularity of the non-metal portion 80 is calculated by the following equation (1) based on the area of the non-metal portion 80 and the circumference (the length of the outline) of the non-metal portion 80.
A set of non-metal portions 80 having a circularity of about 0.4 or less among all the non-metal portions 80 (excluding those having an area of less than about 2.0 μm2 as described above) identified in the analysis target range of the reflected electron images acquired at the four locations of the reflected electron image acquisition positions R1, R2, R3, and R4 is set as the first population. The average area of the non-metal portions 80 in the first population is calculated based on the area of each non-metal portion 80 of the first population.
Based on the area of the analysis target range and the area of the non-metal portion 80, the proportion of the non-metal portion 80 existing in the base electrode layer 50 is calculated by the following equation (2). Proportion (%) of the non-metal portion=(area of the non-metal portion/area of the analysis target range)×100 (2)
For each of the four analysis target ranges (R1, R2, R3, and R4), the proportion of the non-metal portions 80 is calculated. Then, the average value is calculated as the proportion of the non-metal portion 80 of the present example embodiment.
As described above, the measurement target range for calculating the average area of the non-metal portions 80 existing in the first population of the non-metal portions 80 having a circularity of about 0.4 or less is a set of the analysis target ranges at the four locations (R1, R2, R3, and R4) described above. Specifically, the measurement target ranges are portions adjacent to the first main surface TS1 and portions adjacent to the second main surface TS2 of the first base electrode layer 50A and the second base electrode layer 50B, which are in contact with the inner layer portion 11 of the multilayer body 10. More specifically, the measurement target ranges are a portion, in the first base electrode layer 50A and the second base electrode layer 50B, from the position of the boundary portion in the lamination direction between the inner layer portion 11 and the first main surface-side outer layer portion 12 of the multilayer body 10 to the position about 80 μm toward the center in the lamination direction of the multilayer body 10, and a portion, in the first base electrode layer 50A and the second base electrode layer 50B, from the position of the boundary portion in the lamination direction between the inner layer portion 11 and the second main surface-side outer layer portion 13 of the multilayer body 10 to the position about 80 μm toward the center in the lamination direction of the multilayer body 10.
Next, an example of a method of manufacturing the multilayer ceramic capacitor 1 of the present example embodiment will be described. The method of manufacturing the multilayer ceramic capacitor 1 of the present example embodiment is not limited as long as it satisfies the above-described requirements. However, a preferred manufacturing method includes the following steps, for example. The details of each step will be described below.
A dielectric sheet for manufacturing the dielectric layer 20 and an electrically conductive paste for manufacturing the internal electrode layer 30 are prepared. Both of the dielectric sheet for the dielectric layer 20 and the electrically conductive paste for the internal electrode layer 30 include a binder and a solvent. The binders and solvents may be known. The paste made of an electrically conductive material is, for example, a paste obtained by adding an organic binder and an organic solvent to metal powder.
An electrically conductive paste for manufacturing the internal electrode layer 30 is printed on the dielectric sheet by using a printing plate designed to have the shape of the internal electrode layer 30 of the present example embodiment, for example, by screen printing or gravure printing. With such a configuration, a dielectric sheet having a pattern of the first internal electrode layer 31 provided thereon and a dielectric sheet having a pattern of the second internal electrode layer 32 provided thereon are prepared.
By laminating a predetermined number of dielectric sheets on which patterns of the internal electrode layers 30 are not printed, a portion functioning as the first main surface side-outer layer portion 12 adjacent to the first main surface TS1 is formed. On top of that, the dielectric sheets on which the pattern of the first internal electrode layer 31 is printed and the dielectric sheets on which the pattern of the second internal electrode layer 32 is printed are sequentially and alternately laminated to form a portion functioning as the inner layer portion 11. A predetermined number of dielectric sheets on which patterns of the internal electrode layers 30 are not printed are laminated on the portion functioning as the inner layer portion 11 to form a portion functioning as the second main surface side-outer layer portion 13 adjacent to the second main surface TS2. Thus, a multilayer sheet is obtained.
Next, the multilayer sheet is pressed in the laminating direction by, for example, hydrostatic pressing to prepare a multilayer block.
Next, the multilayer block is cut to a predetermined size and divided into individual pieces to obtain a plurality of multilayer chips. Thereafter, the multilayer chips may be polished by, for example, barrel polishing or the like to round the corner portions and the ridge portions.
Next, the multilayer chips are fired to obtain the multilayer body 10. The firing temperature at this time depends on the materials of the dielectric layer 20 and the internal electrode layer 30, but is preferably about 900° C. or higher and about 1400° C. or lower, for example.
The electrically conductive paste defining and functioning as the base electrode layer 50 is applied to both end surfaces of the multilayer body 10. In the present example embodiment, the base electrode layer 50 is a fired layer. The fired layer can be formed by, for example, applying an electrically conductive paste containing a glass component and a metal to the multilayer body 10 by a method such as dipping, and then performing firing treatment. The temperature of the firing treatment at this time is, for example, preferably about 700° C. or higher and about 900° C. or lower.
Furthermore, the multilayer chips before firing and the electrically conductive paste applied to the multilayer chip may be fired simultaneously. In such a case, the fired layer is preferably formed by firing a ceramic material added instead of the glass component. At this time, it is particularly preferable to use, as the ceramic material to be added, the same kind of ceramic material as the dielectric layer 20. In this case, an electrically conductive paste is applied to the multilayer chip before firing, and the multilayer chip and the electrically conductive paste applied to the multilayer chip are fired at the same time to form the multilayer body 10 in which the fired layer is formed.
By changing the shape and particle size distribution of the copper powder added to the electrically conductive paste, it is possible to control the circularity of each of the non-metal portions 80 existing in the base electrode layer 50. The circularity of each of the non-metal portions 80 improves with using the spherical powder as the copper powder and sharper particle size distribution of the copper powder. Conversely, the circularity of each of the non-metal portions 80 decreases with using flat powder as the copper powder and a broader particle size distribution of the copper powder.
It is possible to control the average area of the non-metal portions 80 existing in the base electrode layer 50 by changing the particle diameter and firing temperature of the copper powder and the glass component. As the particle diameters of the copper powder and the glass component are smaller and the firing temperature is higher, the average area of the non-metal portion 80 becomes smaller. Conversely, as the particle diameters of the copper powder and the glass component are larger and the firing temperature is lower, the average area of the non-metal portion 80 becomes larger.
It is possible to control the proportion of the non-metal portions 80 existing in the base electrode layer 50 by changing the addition of the glass component and the firing temperature. As the addition of the glass component is larger and the firing temperature is higher, the proportion of the non-metal portions 80 becomes higher. Conversely, as the addition of the glass component is smaller and the firing temperature is lower, the proportion of the non-metal portions 80 becomes lower. The composition of the electrically conductive paste preferably includes, for example, about 50 vol % or more and about 80 vol % or less of the copper powder, about 5 vol % or more and about 20 vol % or less of the glass component, and other solvents and resin components.
Thereafter, the plated layer is formed on the surface of the base electrode layer 50 including the fired layer. In the present example embodiment, the first plated layer 60A is formed on the surface of the first base electrode layer 50A. Furthermore, the second plated layer 60B is formed on the surface of the second base electrode layer 50B. In the present example embodiment, the Ni plated layer and the Sn plated layer are formed as the plated layers. Upon performing the plating process, electrolytic plating or electroless plating may be adopted. However, the electroless plating has a disadvantage in that a pretreatment with a catalyst or the like is necessary in order to improve the plating deposition rate, and thus the process is complicated. Therefore, normally, electrolytic plating is preferably adopted. The Ni plated layer and Sn the plated layer are sequentially formed, for example, by barrel plating.
When the electrically conductive resin layer is provided, the electrically conductive resin layer may cover the fired layer. When the electrically conductive resin layer is provided, an electrically conductive resin paste including, for example, a thermosetting resin and a metal component is applied on the fired layer, and then heat treatment is performed at a temperature of about 250° C. to about 550° C. or higher. Thus, the thermosetting resin is thermally cured to form the electrically conductive resin layer. The atmosphere during the heat treatment is, for example, preferably an N2 atmosphere. Furthermore, in order to prevent scattering of the resin and to prevent oxidation of various metal components, the oxygen concentration is, for example, preferably about 100 ppm or less.
The multilayer ceramic capacitor 1 is manufactured by the manufacturing process described above.
The configuration of the multilayer ceramic capacitor 1 is not limited to the configuration shown in
The multilayer ceramic capacitor 1 shown in
The multilayer ceramic capacitor 1 may be, for example, of two-terminal type including two external electrodes, or may be of multi-terminal type including a large number of external electrodes.
In the example embodiment of the present invention described above, the multilayer ceramic capacitor in which the dielectric layers 20 made of dielectric ceramic is used as a ceramic layer is exemplified as the multilayer ceramic electronic component. However, the multilayer ceramic electronic component of the present disclosure is not limited thereto. For example, the ceramic electronic component of the present invention is also applicable to a piezoelectric component using piezoelectric ceramic as a ceramic layer, and various multilayer ceramic electronic components such as a thermistor using semiconductor ceramic as a ceramic layer. Examples of the piezoelectric ceramic include PZT (lead zirconate titanate) ceramic and the like. Examples of the semiconductor ceramic include spinel ceramic and the like.
The multilayer ceramic capacitor 1 according to the example embodiment described above achieves the following advantageous effects.
The multilayer ceramic capacitor 1 according to an example embodiment of the present invention includes the multilayer body 10 including the dielectric layers 20 defining and functioning as the plurality of ceramic layers and the internal electrode layers 30 defining and functioning as the plurality of internal conductive layers which are alternately laminated therein in the lamination direction T, the first main surface TS1 and the second main surface TS2 which are opposed to each other in the lamination direction T, the first end surface LS1 and the second end surface LS2 which are opposed to each other in the length direction L perpendicular or substantially perpendicular to the lamination direction T, and the first lateral surface WS1 and the second lateral surface WS2 which are opposed to each other in the width direction W perpendicular or substantially perpendicular to the lamination direction T and the length direction L; and the pair of external electrodes 40 provided on both ends of the multilayer body 10 in the length direction L and spaced apart from each other, in which the plurality of internal electrode layers 30 include the first internal electrode layers 31 each extending toward and exposed at the first end surface LS1, and the second internal electrode layers 32 each extending toward and exposed at the second end surface LS2, in which the pair of external electrodes 40 include the first external electrode 40A including the first base electrode layer 50A connected to the first internal electrode layer 31, and the second external electrode 40B including the second base electrode layer 50B connected to the second internal electrode layer 32, in which the first base electrode layer 50A and the second base electrode layer 50B each include the metal portion 70 and the plurality of non-metal portions 80 existing in the metal portion 70, and in which, in a cross sectional view perpendicular or substantially perpendicular to the width direction W, the average area of a plurality of non-metal portions 80 in the first population of a plurality of non-metal portions 80 each having a circularity of about 0.4 or less is about 10 μm2 or more, and in a cross sectional view perpendicular or substantially perpendicular to the width direction, a proportion of the plurality of non-metal portions in each of the first base electrode layer and the second base electrode layer is about 8.2% or more.
With such a configuration, it is possible to provide a multilayer ceramic capacitor having high crack resistance by obtaining an advantageous effect of stress relaxation with respect to a force applied to the external electrode.
In the multilayer ceramic capacitor 1 according to an example embodiment, it is preferable that the first base electrode layer 50A and the second base electrode layer 50B are each a fired layer.
With such a configuration, it is possible to form the first base electrode layer 50A and the second base electrode layer 50B by a relatively simple method as compared with a case of forming the first base electrode layer 50A and the second base electrode layer 50B by a thin film formation method such as a sputtering method or a deposition method. Furthermore, by forming the fired layer simultaneously with the firing of the multilayer body 10, it is possible to simplify the manufacturing process.
The present invention is not limited to the configurations of the above example embodiment, and can be appropriately modified and applied without departing from the scope of the present invention. The present invention also includes combinations of two or more of the individual desirable configurations described in the above example embodiments.
Examples are described below. According to the manufacturing method described in the example embodiment of the present invention, multilayer ceramic capacitors of a plurality of lots manufactured so that the average area of non-metal portions in the first population in the base electrode layer became different values were manufactured as samples of Examples 1 to 6 and the Comparative Examples. Examples 1 to 6 were directed to multilayer ceramic capacitors that satisfy the example embodiment of the present invention, and the Comparative Example were directed to multilayer ceramic capacitors that do not satisfy the example embodiment of the present invention. Samples of the same lot were manufactured under the same manufacturing conditions, and the specifications of the base electrode layers were the same. Seventy-two samples were prepared for each lot (Examples 1 to 6 and Comparative Example). Next, the manufactured samples of the Examples 1 to 6 and the Comparative Example were subjected to a weight drop test. The weight drop test is performed with the configuration as shown in
In the manufacturing, each sample was manufactured according to the following specifications.
Table 1 shows the measurement results of the average area of the non-metal portions in the first population and the proportion of the non-metal portions existing in the base electrode layer of the samples of the Examples 1 to 6 and the Comparative Example. The measurement results were each an average value of 10 samples prepared separately from the 72 samples.
First, as shown in
The observation of cracks was performed with a microscope while starting polishing from the first lateral surface or the second lateral surface of the multilayer ceramic capacitor and exposing the LT cross section each time from the position where the internal electrode layer started to be exposed at the position where the internal electrode layer ended to be exposed. Here, the number of cracks was counted by distinguishing between the number of cracks present in the active portion and the number of cracks present but not present in the active portion. These results are shown in Table 1.
As apparent in the Comparative Example from Table 1, when the average area of the non-metal portions existing in the first population is less than about 10 μm2, samples having a crack resistance of NG occur. On the other hand, as in the Examples 1 to 6, when the average area of the non-metal portions existing in the first population is about 10 μm2 or more, there are no cracks that have reached the active portion, and therefore, the result of crack resistance is good. Therefore, for example, the average area of the non-metal portions existing in the first population is preferably about 10 μm2 or more in order to maintain crack resistance. The proportion of the non-metal portions in the first population is, for example, also preferably about 8.2% or more, similarly to the average area, in order to maintain crack resistance.
In addition, in Example 1, no samples were generated in which cracks reached the active portion and which had crack resistance of NG, but samples were generated in which cracks occurred but did not reach the active portion. Therefore, it can be evaluated that the average area of the non-metal portions existing in the first population is, for example, more preferably 10.5 μm2 or more. It can be evaluated that the proportion of the non-metal portions existing in the first population is, for example, more preferably about 11% or more.
For example, the average area of the non-metal portions of the first population is preferably about 10 μm2 or more and about 23 μm2 or less, and more preferably about 10.5 μm2 or more and about 23 μm2 or less. As a result, crack resistance is improved.
The proportion of the non-metal portions existing in the base electrode layer is, for example, preferably about 8.2% or more and about 25% or less. For example, the proportion of the non-metal portions existing in the base electrode layer is preferably about 11% or more and about 25% or less.
While example embodiments of the present invention have been described above, it is to be understood that variations and modifications will be apparent to those skilled in the art without departing from the scope and spirit of the present invention. The scope of the present invention, therefore, is to be determined solely by the following claims.
Number | Date | Country | Kind |
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2022-144856 | Sep 2022 | JP | national |
This application is a Continuation Application of PCT Application No. PCT/JP2023/021220 filed on Jun. 7, 2023, and claims the benefit of priority to Japanese Patent Application No. 2022-144856, filed on Sep. 12, 2022. The entire contents of each application are hereby incorporated herein by reference.
Number | Date | Country | |
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Parent | PCT/JP2023/021220 | Jun 2023 | WO |
Child | 18818715 | US |