Multilayer ceramic capacitor

Abstract

Provided is a multilayer ceramic capacitor in which a dense ceramic layer is formed while ensuring sinterability, and which comprises high moisture resistance reliability.　The present invention specifically provides a multilayer ceramic capacitor 1 wherein, in a cross section that extends in the multilayer (T) direction and the width (W) direction of a multilayer body 10, the content of calcium silicate is higher in outer side margin parts 41o, 42o than in inner side margin parts 41i, 42i, and is higher in outer outside layer parts 31o, 32o than in inner outside layer parts 31i, 32i, while the content of a Ca-Mn-Si-based oxide is higher in the inner side margin parts 41i, 42i than in the outer side margin parts 41o, 42o, and is higher in the inner outside layer parts 31i, 32i than in the outer outside layer parts 32i, 32o.

Description

Multilayer ceramic capacitors

[0001] The present invention relates to a multilayer ceramic capacitor.

[0002] In recent years, with the miniaturization of electronic devices, there has been a demand for miniaturization of electronic components having a laminated structure (hereinafter also referred to as multilayer ceramic capacitors) mounted on circuit boards. Conventionally, in order to reduce dielectric loss and improve performance in the high frequency range, a technique has been known for multilayer ceramic capacitors to obtain a high Q value (high Q value = low energy loss within the capacitor) by using a dielectric ceramic having a perovskite structure containing Ca and Zr as the main phase (see, for example, Patent Document 1).

[0003] However, CaZrO ３ In multilayer ceramic capacitors using dielectric ceramics containing Cr-based ceramics, the growth of ceramic particles during firing of a green chip varies depending on the region of the multilayer ceramic capacitor, and the average grain size tends to be larger in the outer layer or side margin regions than in the inner layer regions, as in Patent Document 1, for example. If the average grain size in the outer layer or side margin regions is larger, stress release tends to progress when intergranular corrosion progresses, that is, when the grain boundaries are eroded, which tends to lead to a decrease in moisture resistance due to the generation of cracks.

[0004] On the other hand, if an attempt is made to reduce the average grain size of the dielectric ceramic constituting the outer layer portion or the side margin portion, it becomes difficult to ensure the sinterability of the multilayer ceramic capacitor, and pores tend to remain in the region close to the inner layer portion, which tends to reduce moisture resistance and strength.

[0005] Therefore, there is a need to develop a multilayer ceramic capacitor that can form dense ceramic layers while ensuring sinterability and has high moisture resistance reliability.

[0006] Japanese Patent Application Laid-Open No. 2019-102752

[0007] An object of the present invention is to provide a multilayer ceramic capacitor in which dense ceramic layers are formed while ensuring sinterability and which has high moisture resistance reliability.

[0008] The present inventors have discovered that the moisture resistance of a multilayer ceramic capacitor can be improved by making the calcium silicate content in the outer side margin portion greater than the calcium silicate content in the inner side margin portion in a cross section extending in the stacking direction and width direction of the laminate constituting the multilayer ceramic capacitor, and have thus completed the present invention.

[0009] That is, the present invention provides a laminate including a plurality of dielectric layers and a plurality of internal electrode layers alternately stacked along a stacking direction, and having first and second main faces opposing each other in the stacking direction, first and second side faces opposing each other in a width direction perpendicular to the stacking direction, and first and second end faces opposing each other in a length direction perpendicular to both the stacking direction and the width direction; a first external electrode provided on the first end face, and connected to end portions of the plurality of internal electrode layers; and a second external electrode provided on the second end face, and connected to end portions of the plurality of internal electrode layers, the laminate comprises an inner layer portion in which the plurality of internal electrode layers face each other to form a capacitance, a first outer layer portion located on a first main surface side of the inner layer portion in the lamination direction, a second outer layer portion located on a second main surface side of the inner layer portion in the lamination direction, a first side margin portion located on a first side surface side of the inner layer portion and on a first side surface side of the first outer layer portion in the width direction, and a second side margin portion located on a second side surface side of the inner layer portion and on a second side surface side of the second outer layer portion in the width direction, the first side margin portion and the second side margin portion have an outer side margin portion located on the first side surface side or the second side surface side, and an inner side margin portion located closer to the inner layer portion than the outer side margin portion, and in a cross section of the laminate extending in the lamination direction and the width direction, the calcium silicate content in the outer side margin portion is greater than the calcium silicate content in the inner side margin portion, the content of Ca-Mn-Si-based oxides in the inner side margin portion is greater than the content of Ca-Mn-Si-based oxides in the outer side margin portion; the first outer layer portion and the second outer layer portion have an outer outer layer portion located on the first main surface side or the second main surface side, and an inner outer layer portion located closer to the inner layer portion than the outer outer layer portion; in a cross section of the laminate extending in the stacking direction and the width direction, the content of calcium silicate in the outer outer layer portion is greater than the content of calcium silicate in the inner outer layer portion; and the content of Ca-Mn-Si-based oxides in the inner outer layer portion is greater than the content of Ca-Mn-Si-based oxides in the outer outer layer portion.

[0010] According to the present invention, dense ceramic layers are formed while ensuring sinterability, and it is possible to provide a multilayer ceramic capacitor having high moisture resistance reliability.

[0011] FIG. 1 is a schematic external view showing a multilayer ceramic capacitor of the present invention; FIG. 2 is a schematic external view showing a laminate of the multilayer ceramic capacitor of the present invention; FIG. 3 is a cross-sectional view taken along line III-III of the multilayer ceramic capacitor of the present invention; FIG. 4 is a cross-sectional view taken along line IV-IV of the multilayer ceramic capacitor of the present invention; FIG. 5 is a cross-sectional view taken along line V-V of the multilayer ceramic capacitor of the present invention; FIG. 6 is a diagram illustrating a manufacturing process (first embodiment) of the multilayer ceramic capacitor of the present invention; FIG. 7 is a diagram illustrating a manufacturing process (first embodiment) of the multilayer ceramic capacitor of the present invention; FIG. 8 is a diagram illustrating a manufacturing process (first embodiment) of the multilayer ceramic capacitor of the present invention; FIG. 9 is a diagram illustrating a manufacturing process (first embodiment) of the multilayer ceramic capacitor of the present invention; FIG. 10 is a diagram illustrating a manufacturing process (first embodiment) of the multilayer ceramic capacitor of the present invention; FIG. 11 is a diagram illustrating a manufacturing process (first embodiment) of the multilayer ceramic capacitor of the present invention; FIG. 12 is a diagram illustrating a manufacturing process (second embodiment) of the multilayer ceramic capacitor of the present invention; FIG. 13 is a diagram illustrating a manufacturing process (second embodiment) of the multilayer ceramic capacitor of the present invention.

[0012] Hereinafter, embodiments of the present invention will be described. The embodiments are illustrative of the present invention, and the present invention is not limited to the contents of the embodiments. It is also possible to combine the contents described in different embodiments, and such implementations are also included in the present invention. The drawings are intended to aid understanding of the specification and may be drawn schematically, and the dimensional ratios of the depicted components or between the components may not match the dimensional ratios of those components described in the specification. Components described in the specification may be omitted in the drawings, or the number of components may be omitted.

[0013] Fig. 1 is a perspective view schematically showing an example of a multilayer ceramic capacitor of the present invention. Fig. 2 is a perspective view schematically showing an example of a laminate constituting the multilayer ceramic capacitor shown in Fig. 1. Fig. 3 is a cross-sectional view taken along line III-III of the multilayer ceramic capacitor shown in Fig. 1. Fig. 4 is a cross-sectional view taken along line IV-IV of the multilayer ceramic capacitor shown in Fig. 1.

[0014] In this specification, the lamination direction, width direction, and length direction of the multilayer ceramic capacitor and laminate are defined by arrows T, W, and L, respectively, in the multilayer ceramic capacitor 1 shown in FIG. 1 and the laminate 10 shown in FIG. 2. In the embodiment, the lamination (T) direction, width (W) direction, and length (L) direction are perpendicular to each other, but they are not necessarily perpendicular to each other and may intersect each other. The lamination (T) direction is the direction in which the multiple dielectric layers 20 and the multiple internal electrode layers 21 are stacked.

[0015] The multilayer ceramic capacitor 1 shown in FIG. 1 includes a laminate 10 and a pair of external electrodes, a first external electrode 51 and a second external electrode 52 , provided on both end surfaces of the laminate 10 .

[0016] As shown in FIG. 2 , the laminate 10 has a rectangular or approximately rectangular parallelepiped shape, and has a first main surface 11 and a second main surface 12 that face each other in the stacking (T) direction, a first side surface 13 and a second side surface 14 that face each other in the width (W) direction perpendicular to the stacking (T) direction, and a first end surface 15 and a second end surface 16 that face each other in the length (L) direction perpendicular to the stacking (T) direction and the width (W) direction.

[0017] In this specification, a cross section of the multilayer ceramic capacitor 1 or laminate 10 that is orthogonal to the first end face 15 and the second end face 16 and parallel to the stacking (T) direction is referred to as an LT cross section, which is a cross section extending in the length (L) direction and the stacking (T) direction. A cross section of the multilayer ceramic capacitor 1 or laminate 10 that is orthogonal to the first side face 13 and the second side face 14 and parallel to the stacking (T) direction is referred to as a WT cross section, which is a cross section extending in the width (W) direction and the stacking (T) direction. A cross section of the multilayer ceramic capacitor 1 or laminate 10 that is orthogonal to the first side face 13, the second side face 14, the first end face 15, and the second end face 16 and perpendicular to the stacking (T) direction is referred to as an LW cross section, which is a cross section extending in the length (L) direction and the width (W) direction. Therefore, FIG. 3 shows an LT cross section of the multilayer ceramic capacitor 1, and FIG. 4 shows a WT cross section of the multilayer ceramic capacitor 1.

[0018] It is preferable that the corners and ridges of the laminate 10 are rounded. A corner is a portion where three surfaces of the laminate intersect, and a ridge is a portion where two surfaces of the laminate intersect.

[0019] 2, 3, and 4, the laminate 10 has a laminated structure in which a plurality of dielectric layers 20 and a plurality of internal electrode layers 21 are laminated in the lamination (T) direction. The internal electrode layers 21 include first internal electrode layers 21a and second internal electrode layers 21b, and the dielectric layers 20 are disposed between the first internal electrode layers 21a and the second internal electrode layers 21b.

[0020] Fig. 5 is an LW cross section taken along line V-V of the multilayer ceramic capacitor shown in Fig. 1. The dielectric layers 20 extend in the width (W) and length (L) directions, and the first internal electrode layers 21a and the second internal electrode layers 21b each extend in a flat plate shape along the dielectric layers 20.

[0021] The first internal electrode layer 21 a is extended to a first end face 15 of the laminate 10 , while the second internal electrode layer 21 b is extended to a second end face 16 of the laminate 10 .

[0022] The first internal electrode layer 21a and the second internal electrode layer 21b face each other in the stacking (T) direction via the dielectric layer 20. Electrostatic capacitance is generated by the portion where the first internal electrode layer 21a and the second internal electrode layer 21b face each other via the dielectric layer 20.

[0023] Each of the first internal electrode layer 21a and the second internal electrode layer 21b preferably contains a metal such as Ni, Cu, Ag, Pd, an Ag-Pd alloy, Au, etc. Each of the first internal electrode layer 21a and the second internal electrode layer 21b may contain the same dielectric ceramic material as the dielectric layer 20 in addition to the above metals.

[0024] The dielectric layer 20 is made of a dielectric ceramic containing a perovskite-type compound containing Ca and Zr. Such a dielectric ceramic is CaCO ３ , SrCO ３ , BaCO ３ , TiO ２ , ZrO ２ The powder obtained by mixing powders such as SiO and the like, calcining the mixture, and then pulverizing the mixture can be used as the main ceramic raw material. ２ , MnCO ３ etc. can be added.

[0025] The first external electrode 51 is provided on the first end surface 15 of the laminate 10, and in Fig. 1 has a portion that extends around to each of the first main surface 11, the second main surface 12, the first side surface 13, and the second side surface 14. The first external electrode 51 is connected to the first internal electrode layer 21a at the first end surface 15.

[0026] The second external electrode 52 is provided on the second end surface 16 of the laminate 10, and in Fig. 1 has a portion that extends around to each of the first main surface 11, the second main surface 12, the first side surface 13, and the second side surface 14. The second external electrode 52 is connected to the second internal electrode layer 21b at the second end surface 16.

[0027] The first external electrode 51 and the second external electrode 52 can be formed, for example, by a base electrode layer and a plating layer disposed on the base electrode layer. The base electrode layer is formed by applying a conductive paste containing a metal component and a glass component to the first end surface 15 and the second end surface 16 of the laminate 10, followed by baking. Examples of the metal component contained in the conductive paste include metals such as Cu, Ni, Ag, Pd, and Au, and alloys of Ag and Pd. Examples of the glass component contained in the conductive paste include B-Si glass, Ba-B-Si glass, B-Si-Zn glass, B-Si-Zn-Ba glass, and B-Si-Zn-Ba-Ca-Al glass.

[0028] The plating layer disposed on the base electrode layer includes at least one of metals such as Cu, Ni, Ag, Pd, and Au, or an alloy of Ag and Pd. The plating layer may have a two-layer structure, for example, a Ni plating layer and a Sn plating layer. However, the plating layer may be a single layer or multiple layers. Furthermore, a resin electrode layer containing, for example, conductive particles and a thermosetting resin may be disposed between the base electrode layer and the plating layer.

[0029] As shown in Figures 2, 3, and 4, the laminate 10 includes an inner layer portion 30 in which the dielectric layers 20, the first internal electrode layers 21a, and the second internal electrode layers 21b are stacked, a pair of first outer layer portions 31 and second outer layer portions 32 arranged to sandwich the inner layer portion 30 in the stacking (T) direction, and a pair of first side margin portions 41 and second side margin portions 42 arranged to sandwich the inner layer portion 30, the first outer layer portion 31, and the second outer layer portion 32 in the width (W) direction.

[0030] 3 and 4, the inner layer portion 30 is a region sandwiched between the first inner electrode layer 21a closest to the first main surface 11 and the first inner electrode layer 21a closest to the second main surface 12 along the stacking (T) direction.

[0031] A first outer layer portion 31 and a second outer layer portion 32 are provided to sandwich the inner layer portion 30 in the stacking (T) direction. The first outer layer portion 31 is located on the first main surface 11 side of the laminate 10, and the second outer layer portion 32 is located on the second main surface 12 side of the laminate 10. The inner layer portion 30 is a region where the first internal electrode layer 21a and the second internal electrode layer 21b face each other.

[0032] The first outer layer portion 31 may have a two-layer structure laminated in the stacking (T) direction, and may be composed of an outer outer layer portion 31o located on the first main surface 11 side and an inner outer layer portion 31i located closer to the inner layer portion 30 than the outer outer layer portion 31o. The second outer layer portion 32 may have a two-layer structure laminated in the stacking (T) direction, and may be composed of an outer outer layer portion 32o located on the second main surface 12 side and an inner outer layer portion 32i located closer to the inner layer portion 30 than the outer outer layer portion 32o. The thicknesses in the stacking (T) direction of the outer outer layer portion 31o and the inner outer layer portion 31i constituting the first outer layer portion 31 may be approximately the same, or the thicknesses in the stacking (T) direction of the outer outer layer portion 31o and the inner outer layer portion 31i may be different. The thicknesses in the stacking (T) direction of the outer outer layer portion 32o and the inner outer layer portion 32i that make up the second outer layer portion 32 may be approximately the same, or the thicknesses in the stacking (T) direction of the outer outer layer portion 32o and the inner outer layer portion 32i may be different.

[0033] Furthermore, the thickness of the outer outer layer portion 31o in the stacking direction is preferably greater than the thickness of the inner outer layer portion 31i. Specifically, the thickness of the outer outer layer portion 31o in the stacking (T) direction is preferably 10 μm or more and 30 μm or less. If the thickness of the outer outer layer portion 31o in the stacking (T) direction is less than 10 μm, the outer outer layer portion 31o may not contain enough calcium silicate. If the outer outer layer portion 31o does not contain enough calcium silicate, few crystals may be formed in the outer outer layer portion 31o. If few crystals are formed in the outer outer layer portion 31o, the area containing the crystals in the outer outer layer portion 31o becomes smaller, and the area containing the sintering aid in the outer outer layer portion 31o becomes larger. In other words, the content of the sintering aid in the outer outer layer portion 31o increases. Because sintering aids are inherently vulnerable to moisture, etc., a high content of sintering aid in the outer layer portion 31o can potentially allow moisture, etc., to penetrate into the outer layer portion 31o from the outside. As a result, moisture, etc., can penetrate into the outer layer portion 31o from the outside. If moisture, etc., penetrates the inner layer portion 30 via the outer layer portion 31o, a short circuit can occur, potentially reducing the moisture resistance reliability of the multilayer ceramic capacitor 1. When the thickness of the outer layer portion 31o in the lamination (T) direction is greater than 30 μm, the outer layer portion 31o may contain a large amount of calcium silicate. When a large amount of calcium silicate is contained in the outer layer portion 31o, a large amount of crystals may form in the outer layer portion 31o. When a large amount of crystals form in the outer layer portion 31o, the area containing the crystals in the outer layer portion 31o increases, and the area containing the sintering aid in the outer layer portion 31o decreases. That is, the amount of sintering aid contained in the outer layer portion 31 o decreases. The sintering aid contained in the outer layer portion 31 o has the function of improving the sinterability of the outer layer portion 31 o when the laminate 10 is fired, but if the amount of sintering aid contained in the outer layer portion 31 o decreases, the outer layer portion 31 o will not be sintered sufficiently, and there is a possibility that the sinterability of the outer layer portion 31 o will not be ensured.As a result, the outer outer layer portion 31o is insufficiently sintered in a region close to the inner layer portion 30 of the outer outer layer portion 31o, which is less susceptible to the heat during firing, and pores are likely to remain in the region close to the inner layer portion 30 of the outer outer layer portion 31o, which may allow moisture or the like to penetrate from the outside into the pores in the region close to the inner layer portion 30 of the outer outer layer portion 31o. As a result, if moisture or the like penetrates into the inner layer portion 30 through the pores in the region close to the inner layer portion 30 of the outer outer layer portion 31o, a short circuit will occur, and the moisture resistance reliability of the multilayer ceramic capacitor 1 may not be ensured.

[0034] Furthermore, the thickness of the inner outer layer portion 31i in the stacking (T) direction is preferably 5 μm or more and 20 μm or less. If the thickness of the inner outer layer portion 31i in the stacking (T) direction is less than 5 μm, the inner outer layer portion 31i may not contain enough calcium silicate. If the inner outer layer portion 31i does not contain enough calcium silicate, few crystals may be formed in the inner outer layer portion 31i. If few crystals are formed in the inner outer layer portion 31i, the area containing the crystals in the inner outer layer portion 31i becomes smaller, and the area containing the sintering aid in the inner outer layer portion 31i becomes larger. In other words, the content of the sintering aid in the inner outer layer portion 31i increases. Since sintering aids are inherently vulnerable to moisture, etc., if the content of the sintering aid in the outer outer layer portion 31i increases, moisture, etc. may penetrate into the inner outer layer portion 31i from the outside. As a result, moisture and the like may penetrate the inner outer layer portion 31i from the outside. If moisture and the like penetrates the inner layer portion 30 via the inner outer layer portion 31i, a short circuit may occur, which may reduce the moisture resistance reliability of the multilayer ceramic capacitor 1. When the thickness of the inner outer layer portion 31i in the lamination (T) direction is greater than 20 μm, the outer outer layer portion 31i may contain a large amount of calcium silicate. When the inner outer layer portion 31i contains a large amount of calcium silicate, many crystals may form within the inner outer layer portion 31i. When many crystals form within the inner outer layer portion 31i, the area containing the crystals within the inner outer layer portion 31i increases, and the area containing the sintering aid within the inner outer layer portion 31i decreases. In other words, the amount of sintering aid contained within the inner outer layer portion 31i decreases. The sintering aid in the inner outer layer portion 31i has the function of improving the sinterability of the inner outer layer portion 31i when the laminate 10 is fired, but if the content of the sintering aid in the inner outer layer portion 31i is reduced, the inner outer layer portion 31i will not be sintered sufficiently, and there is a possibility that the sinterability of the inner outer layer portion 31i will not be ensured. As a result, the region of the inner outer layer portion 31i near the inner layer portion 30 of the inner outer layer portion 31i, which is less affected by the heat during firing, will be insufficiently sintered, and pores will likely remain in the region of the inner outer layer portion 31i near the inner layer portion 30, which may allow moisture and the like to penetrate from the outside into the pores in the region of the inner outer layer portion 31i near the inner layer portion 30.As a result, if moisture or the like penetrates into the inner layer portion 30 through the pores in the region of the inner outer layer portion 31i close to the inner layer portion 30, a short circuit may occur, and the moisture resistance reliability of the multilayer ceramic capacitor 1 may not be ensured.

[0035] By adjusting the thickness of the outer outer layer portion 31o in the stacking (T) direction to 10 μm or more and 30 μm or less, the thickness of the outer outer layer portion 31o in the stacking (T) direction is greater than the thickness of the inner outer layer portion 31i in the stacking (T) direction, allowing the outer outer layer portion 31o to contain more calcium silicate than the inner outer layer portion 31i. This makes it possible to ensure a balance between the crystals formed in the outer outer layer portion 31o and the content of the sintering aid. By ensuring a balance between the crystals formed in the outer outer layer portion 31o and the content of the sintering aid, the outer outer layer portion 31o can ensure the denseness and sinterability of the outer outer layer portion 31o. As a result, it is possible to form a dense outer outer layer portion 31o while ensuring the sinterability of the outer outer layer portion 31o. This reduces the possibility of moisture or the like penetrating the outer outer layer portion 31o from the outside, thereby achieving a multilayer ceramic capacitor 1 with high moisture resistance reliability.

[0036] Similarly, by adjusting the thickness of the inner outer layer portion 31i in the stacking (T) direction to 5 μm or more and 20 μm or less, the thickness of the inner outer layer portion 31i in the stacking (T) direction is thinner than the thickness of the outer outer layer portion 31o in the stacking (T) direction, allowing the inner outer layer portion 31i to contain less calcium silicate than the outer outer layer portion 31o. This makes it possible to ensure a balance between the crystals formed in the inner outer layer portion 31i and the content of the sintering aid. By ensuring a balance between the crystals formed in the inner outer layer portion 31i and the content of the sintering aid, the inner outer layer portion 31i can ensure its denseness and sinterability. Ensuring the sinterability of the inner outer layer portion 31i reduces the likelihood of pores remaining in the region close to the inner layer portion 30. As a result, pores are less likely to remain in the region of the inner outer layer portion 31i close to the inner layer portion 30, reducing the possibility of moisture or the like penetrating from the outside, allowing for the formation of dense inner outer layer portions 31i while ensuring sinterability, thereby achieving a multilayer ceramic capacitor 1 with high moisture resistance reliability. The thickness of the first outer layer portion 31 after firing is preferably 15 μm or more and 40 μm or less.

[0037] Similarly, the second outer layer portion 32 may have a two-layer structure laminated in the stacking (T) direction, and may be composed of an outer outer layer portion 32o located on the second main surface 12 side and an inner outer layer portion 32i located closer to the inner layer portion 30 than the outer outer layer portion 32o. The second outer layer portion 32 may have a two-layer structure laminated in the stacking (T) direction, and may be composed of an outer outer layer portion 32o located on the second main surface 12 side and an inner outer layer portion 32i located closer to the inner layer portion 30 than the outer outer layer portion 32o. The thicknesses in the stacking (T) direction of the outer outer layer portion 32o and the inner outer layer portion 32i constituting the first outer layer portion 32 may be approximately the same, or the thicknesses in the stacking (T) direction of the outer outer layer portion 32o and the inner outer layer portion 32i may be different. The thicknesses in the stacking (T) direction of the outer outer layer portion 32o and the inner outer layer portion 32i that make up the second outer layer portion 32 may be approximately the same, or the thicknesses in the stacking (T) direction of the outer outer layer portion 32o and the inner outer layer portion 32i may be different.

[0038] Furthermore, the thickness of the outer outer layer portion 32o in the stacking direction is preferably greater than the thickness of the inner outer layer portion 32i. Specifically, the thickness of the outer outer layer portion 32o in the stacking (T) direction is preferably 10 μm or more and 30 μm or less. If the thickness of the outer outer layer portion 32o in the stacking (T) direction is less than 10 μm, the outer outer layer portion 32o may not contain enough calcium silicate. If the outer outer layer portion 32o does not contain enough calcium silicate, few crystals may be formed in the outer outer layer portion 32o. If few crystals are formed in the outer outer layer portion 32o, the area containing the crystals in the outer outer layer portion 32o becomes smaller, and the area containing the sintering aid in the outer outer layer portion 32o becomes larger. In other words, the amount of sintering aid contained in the outer outer layer portion 32o increases. Because sintering aids are inherently vulnerable to moisture, a high content of sintering aid in the outer layer portion 32o can potentially allow moisture to penetrate the outer layer portion 32o from the outside. Therefore, if moisture penetrates the inner layer portion 30 via the outer layer portion 32o, a short circuit occurs. This can result in a decrease in the moisture resistance reliability of the multilayer ceramic capacitor 1. When the thickness of the outer layer portion 32o in the lamination (T) direction is greater than 30 μm, the outer layer portion 32o may contain a large amount of calcium silicate. When a large amount of calcium silicate is contained in the outer layer portion 32o, a large amount of crystals may form within the outer layer portion 32o. When a large amount of crystals form within the outer layer portion 32o, the area containing the crystals within the outer layer portion 32o increases, resulting in a smaller area containing the sintering aid within the outer layer portion 32o. In other words, the amount of sintering aid contained within the outer layer portion 32o decreases. The sintering aid in the outer outer layer portion 32o has the function of improving the sinterability of the outer outer layer portion 32o when the laminate 10 is fired, but if the content of the sintering aid in the outer outer layer portion 32o becomes low, the outer outer layer portion 32o will not be sintered sufficiently, and it may be impossible to ensure the sinterability of the outer outer layer portion 32o.

[0039] As a result, the outer outer layer portion 32o is insufficiently sintered in a region close to the inner layer portion 30 of the outer outer layer portion 32o, which is less susceptible to the heat during firing, and pores are likely to remain in the region close to the inner layer portion 30 of the outer outer layer portion 32o, which may allow moisture or the like to penetrate from the outside into the pores in the region close to the inner layer portion 30 of the outer outer layer portion 32o. As a result, if moisture or the like penetrates into the inner layer portion 30 through the pores in the region close to the inner layer portion 30 of the outer outer layer portion 32o, a short circuit occurs, and the moisture resistance reliability of the multilayer ceramic capacitor 1 may not be ensured.

[0040] Furthermore, the thickness of the inner outer layer portion 32i in the stacking (T) direction is preferably 5 μm or more and 20 μm or less. If the thickness of the inner outer layer portion 32i in the stacking (T) direction is less than 5 μm, the inner outer layer portion 32i may not contain enough calcium silicate. If the inner outer layer portion 32i does not contain enough calcium silicate, few crystals may be formed in the inner outer layer portion 32i. If few crystals are formed in the inner outer layer portion 32i, the area containing the crystals in the inner outer layer portion 32i becomes smaller, and the area containing the sintering aid in the inner outer layer portion 32i becomes larger. In other words, the content of the sintering aid in the inner outer layer portion 32i increases. Since sintering aids are inherently vulnerable to moisture, etc., if the content of the sintering aid in the inner outer layer portion 32i increases, moisture, etc. may penetrate into the inner outer layer portion 32i from the outside. Therefore, moisture or the like may penetrate the inner outer layer portion 32i from the outside. If moisture or the like penetrates the inner layer portion 30 via the inner outer layer portion 32i, a short circuit may occur. As a result, the moisture resistance reliability of the multilayer ceramic capacitor 1 may be reduced. When the thickness of the inner outer layer portion 32i in the stacking (T) direction is greater than 20 μm, the outer outer layer portion 32i may contain a large amount of calcium silicate. When the inner outer layer portion 32i contains a large amount of calcium silicate, many crystals may form within the inner outer layer portion 32i. When many crystals form within the inner outer layer portion 32i, the area containing the crystals within the inner outer layer portion 32i increases, and the area containing the sintering aid within the inner outer layer portion 32i decreases. In other words, the amount of sintering aid contained within the inner outer layer portion 32i decreases. The sintering aid in the inner outer layer portion 32i has the function of improving the sinterability of the inner outer layer portion 32i when the laminate 10 is fired, but if the content of the sintering aid in the inner outer layer portion 32i is reduced, the inner outer layer portion 32i will not be sintered sufficiently, and there is a possibility that the sinterability of the inner outer layer portion 32i will not be ensured. As a result, the region of the inner outer layer portion 32i near the inner layer portion 30 of the inner outer layer portion 32i, which is less affected by the heat during firing, will be insufficiently sintered, and pores will likely remain in the region of the inner outer layer portion 32i near the inner layer portion 30, which may allow moisture and the like to penetrate from the outside into the pores in the region of the inner outer layer portion 32i near the inner layer portion 30.As a result, if moisture or the like penetrates into the inner layer portion 30 through the pores in the region of the inner outer layer portion 32i close to the inner layer portion 30, a short circuit may occur, and the moisture resistance reliability of the multilayer ceramic capacitor 1 may not be ensured.

[0041] By adjusting the thickness of the outer outer layer portion 32o in the stacking (T) direction to 10 μm or more and 30 μm or less, the thickness of the outer outer layer portion 32o in the stacking (T) direction is greater than the thickness of the inner outer layer portion 32i in the stacking (T) direction, allowing the outer outer layer portion 32o to contain more calcium silicate than the inner outer layer portion 32i. This makes it possible to ensure a balance between the crystals formed in the outer outer layer portion 32o and the content of the sintering aid. By ensuring a balance between the crystals formed in the outer outer layer portion 32o and the content of the sintering aid, the outer outer layer portion 32o can ensure the denseness and sinterability of the outer outer layer portion 32o. As a result, it is possible to form a dense outer outer layer portion 32o while ensuring the sinterability of the outer outer layer portion 32o. This reduces the possibility of moisture or the like penetrating the outer outer layer portion 32o from the outside, thereby achieving a multilayer ceramic capacitor 1 with high moisture resistance reliability.

[0042] Similarly, by adjusting the thickness of the inner outer layer portion 32i in the stacking (T) direction to 5 μm or more and 20 μm or less, the thickness of the inner outer layer portion 32i in the stacking (T) direction is thinner than the thickness of the outer outer layer portion 32o in the stacking (T) direction, allowing the inner outer layer portion 32i to contain less calcium silicate than the outer outer layer portion 32o. This makes it possible to ensure a balance between the crystals formed in the inner outer layer portion 32i and the content of the sintering aid. By ensuring a balance between the crystals formed in the inner outer layer portion 32i and the content of the sintering aid, the inner outer layer portion 32i can ensure its denseness and sinterability. Ensuring the sinterability of the inner outer layer portion 32i reduces the likelihood of pores remaining in the region close to the inner layer portion 30. As a result, pores are less likely to remain in the region of the inner outer layer portion 32i close to the inner layer portion 30, reducing the possibility of moisture or the like penetrating from the outside, allowing dense inner outer layer portions 32i to be formed while ensuring sinterability, thereby achieving a multilayer ceramic capacitor 1 with high moisture resistance reliability. The thickness of the second outer layer portion 32 after firing is preferably 15 μm or more and 40 μm or less.

[0043] The dielectric layers forming the first outer layer portion 31 and the second outer layer portion 32 are made of a dielectric ceramic containing a perovskite-type compound containing Ca and Zr. Such a dielectric ceramic is CaCO ３ , SrCO ３ , BaCO ３ , TiO ２ , ZrO ２ The powder obtained by mixing powders such as these, calcining the mixture, and then pulverizing the mixture can be used as the main ceramic raw material. The main ceramic raw material may contain sintering aids such as Ca, Mn, Si, and SiO ２ , MnCO ３ The following may be added, but is not limited to these.

[0044] The calcium silicate content in the outer outer layer portions 31o and 32o located on the first main surface 11 side or the second main surface 12 side of the laminate 10 is higher than the calcium silicate content in the inner outer layer portions 31i and 32i located on the inner layer portion 30 side. Because the thicknesses of the outer outer layer portions 32i and 32o in the stacking (T) direction are greater than the thicknesses of the inner outer layer portions 31i and 32i in the stacking (T) direction, the calcium silicate content is likely to be higher than in the inner outer layer portions 31i and 32i. This makes it possible to ensure a balance between the crystals formed in the outer outer layer portions 31o and 32o and the content of the sintering aid. As a result, it is possible to form a dense outer outer layer portion 32o while ensuring the sinterability of the outer outer layer portion 32o, thereby achieving a multilayer ceramic capacitor 1 with high moisture resistance reliability.

[0045] Furthermore, because the thicknesses of the inner outer layer portions 31i and 32i in the stacking (T) direction are thinner than the thicknesses of the outer outer layer portions 31o and 32o in the stacking (T) direction, they tend to contain less calcium silicate than the outer outer layer portions 31o and 32o. This makes it possible to ensure a balance between the crystals formed in the inner outer layer portions 31i and 32i and the content of the sintering aid. This ensures better sinterability than the outer outer layer portions 31o and 32o, and therefore reduces the likelihood of pores remaining in the region close to the inner layer portion 30. As a result, dense outer outer layer portions 31o, 32o, inner outer layer portions 31i and 32i are formed while ensuring sinterability. This makes it difficult for moisture and the like to penetrate from the outside into the pores in the region close to the inner layer portion 30, thereby achieving a multilayer ceramic capacitor 1 with high moisture resistance reliability.

[0046] Furthermore, the calcium silicate content in the outer outer layer portions 31o and 32o located on the first main surface 11 side or the second main surface 12 side of the laminate 10 is more preferably 5 Atom % or more and 30 Atom % or less relative to the calcium silicate content in the inner outer layer portions 31i and 32i located on the inner layer portion 30 side. If the calcium silicate content in the outer outer layer portions 31o and 32o is less than 5 Atom % relative to the calcium silicate content in the inner outer layer portions 31i and 32i located on the inner layer portion 30 side, the outer outer layer portions 31o and 32o may not contain enough calcium silicate. If the outer outer layer portions 31o and 32o do not contain enough calcium silicate, few crystals may be formed in the outer outer layer portions 31o and 32o. When fewer crystals are formed in the outer outer layer portions 31o and 32o, the area containing the crystals in the outer outer layer portions 31o and 32o becomes smaller, and the area containing the sintering aid in the outer outer layer portions 31o and 32o becomes larger. In other words, the amount of sintering aid in the outer outer layer portions 31o and 32o increases. Since sintering aids are inherently vulnerable to moisture, a high content of sintering aid in the outer outer layer portions 31o and 32o can result in moisture and other external elements penetrating the outer outer layer portions 31o and 32o. Therefore, moisture and other external elements can penetrate the outer outer layer portions 31o and 32o from the outside. If moisture and other external elements penetrate the inner layer portion 30 via the outer outer layer portions 31o and 32o, a short circuit can occur. This may result in a decrease in the moisture resistance reliability of the multilayer ceramic capacitor 1. When the outer outer layer portion 31o and the outer outer layer portion 32o contain more than 30 Atom % of calcium silicate relative to the calcium silicate content of the inner outer layer portion 31i and the inner outer layer portion 32i located on the inner layer portion 30 side, the outer outer layer portion 31o and the outer outer layer portion 32o may contain a large amount of calcium silicate. When the outer outer layer portion 31o and the outer outer layer portion 32o contain a large amount of calcium silicate, a large amount of crystals may form in the outer outer layer portion 31o and the outer outer layer portion 32o.When a large number of crystals are formed in the outer outer layer portions 31o and 32o, the area containing the crystals in the outer outer layer portions 31o and 32o increases, and the area containing the sintering aid in the outer outer layer portions 31o and 32o decreases. In other words, the amount of sintering aid in the outer outer layer portions 31o and 32o decreases. If the amount of sintering aid in the outer outer layer portions 31o and 32o decreases, the outer outer layer portions 31o and 32o are not sufficiently sintered, which may result in the inability to ensure sintering of the outer outer layer portions 31o and 32o. Therefore, pores are likely to remain in the regions of the outer outer layer portions 31o and 32o near the inner layer portion 30, and moisture or the like may penetrate into the pores in the regions of the outer outer layer portions 31o and 32o near the inner layer portion 30 from the outside. As a result, if moisture or the like penetrates into the inner layer portion 30 through the pores in the outer outer layer portion 31o and the outer outer layer portion 32o in the region close to the inner layer portion 30, a short circuit will occur, and the moisture resistance reliability of the multilayer ceramic capacitor 1 may not be ensured.

[0047] Thus, the thicknesses of the inner outer layer portions 31i and 32i in the stacking (T) direction are thinner than the thicknesses of the outer outer layer portions 31o and 32o in the stacking (T) direction, and therefore tend to contain less calcium silicate than the outer outer layer portions 31o and 32o. Therefore, the inner outer layer portions 31i and 32i ensure a balance between the crystals formed in the inner outer layer portions 31i and 32i and the content of the sintering aid, while ensuring better sinterability than the outer outer layer portions 31o and 32o. This reduces the likelihood of pores remaining in the region close to the inner layer portion 30. As a result, dense ceramic layers are formed while ensuring sinterability, and moisture and the like are less likely to penetrate from the outside into the pores in the region close to the inner layer portion 30. This reduces the likelihood of short circuits, resulting in a multilayer ceramic capacitor 1 with high moisture resistance reliability.

[0048] Although the two-layer structure of the first outer layer 31 and the second outer layer 32 can be observed in a dark field using an optical microscope due to differences in sinterability, depending on the sintering conditions, the outer outer layer 31o and the inner outer layer 31i, or the outer outer layer 32o and the inner outer layer 32i, may become one after firing, making it difficult to recognize the boundary surface. Also, as long as the calcium silicate content can be adjusted in the stacking (T) direction, it is not necessary for the first outer layer 31 and the second outer layer 32 to each have a two-layer structure. That is, for the manufactured multilayer ceramic capacitor 1, in a WT cross section extending in the stacking (T) direction and width (W) direction of the laminate 10, the calcium silicate content in the outer outer layer portion 31o is greater than the calcium silicate content in the inner outer layer portion 31i, and the calcium silicate content in the outer outer layer portion 32o located on the second main surface 12 side is greater than the calcium silicate content in the inner outer layer portion 32i located on the inner layer portion 30 side. Because the thicknesses of the outer outer layer portions 31o and 32o in the stacking (T) direction are greater than the thicknesses of the inner outer layer portions 31i and 32i in the stacking (T) direction, the calcium silicate content is likely to be greater than that of the inner outer layer portions 31i and 32i. Therefore, the crystals formed in the outer outer layer portions 31o and 32o are balanced with the content of the sintering aid, making it easier to form denser outer outer layer portions 31o and 32o. As a result, dense outer outer layer portions 31o and 32o are formed while ensuring sinterability, making it possible to realize a multilayer ceramic capacitor 1 that is less likely to cause short circuits and has high moisture resistance reliability. Furthermore, because the thicknesses of the inner outer layer portions 31i and 32i in the stacking (T) direction are thinner than the thicknesses of the outer outer layer portions 31o and 32o in the stacking (T) direction, they tend to contain less calcium silicate than the outer outer layer portions 31o and 32o. Therefore, the inner outer layer portion 31i and the inner outer layer portion 32i ensure a balance between the crystals formed in the inner outer layer portion 31i and the inner outer layer portion 32i and the content of sintering aid, while ensuring better sinterability than the outer outer layer portion 31o and the outer outer layer portion 32o, so that pores are less likely to remain in the area close to the inner layer portion 30.As a result, dense inner and outer layer portions 31i and 32i are formed while ensuring sinterability, and moisture and the like are less likely to penetrate from the outside into the pores in the area close to the inner layer portion 30, making it less likely for short circuits to occur and enabling the realization of a multilayer ceramic capacitor 1 with high moisture resistance reliability.

[0049] Furthermore, the calcium silicate content in the outer outer layer portion 31o located on the first main surface 11 side is preferably 5 Atom % or more and 30 Atom % or less relative to the calcium silicate content in the inner outer layer portion 31i located on the inner layer portion 30 side. Adjusting the calcium silicate content in the stacking (T) direction of the first outer layer portion 31 in this manner facilitates the calcium silicate content to be greater than that in the inner outer layer portion 31i. This achieves a good balance between the crystals formed in the outer outer layer portion 31o and the content of the sintering aid, facilitating the formation of a denser outer outer layer portion 31o. As a result, a denser outer outer layer portion 31o is formed while ensuring sinterability, resulting in a multilayer ceramic capacitor 1 that is less susceptible to short circuits and has higher moisture resistance reliability.

[0050] Furthermore, the calcium silicate content in the outer outer layer portion 32o located on the second main surface 12 side is preferably 5 Atom % or more and 30 Atom % or less relative to the calcium silicate content in the inner outer layer portion 32i located on the inner layer portion 30 side. By adjusting the calcium silicate content in the stacking (T) direction of the first outer layer portion 32 in this manner, the calcium silicate content is likely to be greater than that in the inner outer layer portion 32i. This achieves a good balance between the crystals formed in the outer outer layer portion 32o and the content of the sintering aid, making it easier to form a denser outer outer layer portion 32o. As a result, a denser outer outer layer portion 32o is formed while ensuring sinterability, making it possible to realize a multilayer ceramic capacitor 1 that is less susceptible to short circuits and has higher moisture resistance reliability.

[0051] (Method for Measuring the Thickness of the Inner Outer Layer Portion 31i, Inner Outer Layer Portion 32i, and Outer Outer Layer Portion 31o and Outer Outer Layer Portion 32o in the Stacking (T) Direction) The thicknesses of the inner outer layer portion 31i, inner outer layer portion 32i, outer outer layer portion 31o, and outer outer layer portion 32o in the stacking (T) direction can be confirmed from the results of a wavelength dispersive X-ray analyzer (hereinafter referred to as WDX). The stacking (T) direction thicknesses of the inner outer layer portion 31i, inner outer layer portion 32i, outer outer layer portion 31o, and outer outer layer portion 32o refer to average values ​​measured at multiple locations along the stacking (T) direction of the first outer layer portion 31 and the second outer layer portion 32. Specifically, first, the cross section of the multilayer ceramic capacitor is polished from the first side surface or second side surface to the center of the multilayer ceramic capacitor in the width direction to expose the LT cross section. Then, the first outer layer portion 31 and the second outer layer portion 32 are observed using WDX. The observation conditions were 1000x magnification and 5 kV acceleration voltage, and images of three locations, the left end, right end, and center, of the first outer layer portion 31 and the second outer layer portion 32, were taken with a field of view of 50 μm × 50 μm. Based on the results of WDX elemental mapping analysis of images taken under the above observation conditions, the thickness of the outer outer layer portion 31o in the stacking (T) direction was determined by measuring the locations containing the most calcium silicate in the length (L) direction of the first outer layer portion 31 and the second outer layer portion 32 from the first main surface 11 and the second main surface 12 of the left end, right end, and center toward the inner layer portion 30 using the scale in the image data obtained by elemental mapping analysis, and calculating the average value. The thickness of the outer outer layer portion 31o in the stacking (T) direction was also obtained using a similar measurement method. The thickness of the inner outer layer portion 31i in the stacking (T) direction is obtained by measuring the distance from the part of the outer outer layer portion 31o in the stacking (T) direction closest to the inner layer portion 30 to the inner layer portion 30 using the scale in the image data obtained by elemental mapping analysis, and calculating the average value. The thickness of the inner outer layer portion 32i in the stacking (T) direction can also be obtained by a similar measurement method.

[0052] (Specific Method for Measuring Calcium Silicate) The calcium silicate content in the inner outer layer portion 31i and inner outer layer portion 32i located on the inner layer portion 30 side of the laminate 10 and the calcium silicate content in the outer outer layer portion 31o and outer outer layer portion 32o located on the first main surface 11 side or the second main surface 12 side can be confirmed from the results of images obtained by elemental mapping analysis using WDX. The calcium silicate content in the inner outer layer portion 31i and inner outer layer portion 32i and the outer outer layer portion 31o and outer outer layer portion 32o refers to the average value measured at multiple locations in the inner outer layer portion 31i and inner outer layer portion 32i along the stacking (T) direction and the average value measured at multiple locations in the outer outer layer portion 31o and outer outer layer portion 32o. Specifically, first, the multilayer ceramic capacitor is cross-sectionally polished from the first side surface or second side surface to the center of the multilayer ceramic capacitor in the width direction to expose the LT cross section. The polished inner outer layer portion 31i, inner outer layer portion 32i, outer outer layer portion 31o, and outer outer layer portion 32o are then observed by WDX. Observation conditions include a magnification of 3000x and an acceleration voltage of 15 kV, and images of three locations (left end, right end, and center) of the inner outer layer portion 31i, inner outer layer portion 32i, and outer outer layer portion 31o and outer outer layer portion 32o are taken with a field of view of 50 μm × 50 μm. Based on the results of elemental mapping analysis using WDX on images taken under the above observation conditions, the calcium silicate content of the inner outer layer portion 31i and inner outer layer portion 32i can be determined by measuring the calcium silicate content of the left end, right end, and center of the inner outer layer portion 31i and inner outer layer portion 32i and calculating the average value. The calcium silicate content of the outer outer layer portion 31o and the outer outer layer portion 32o is obtained by measuring the calcium silicate content of the left end, right end and center of the outer outer layer portion 31o and the outer outer layer portion 32o and calculating the average value.

[0053] Similarly, in a manufactured multilayer ceramic capacitor 1, in a WT cross section extending in the stacking (T) direction and width (W) direction of the laminate 10, the content of Ca—Mn—Si-based oxides in the inner outer layer portion 31i located on the inner layer portion 30 side is greater than the content of Ca—Mn—Si-based oxides in the outer outer layer portion 31o located on the first main surface 11 side. The Ca—Mn—Si-based oxides function as a sintering aid during firing, ensuring the sintering properties of the inner outer layer portion 31i and the inner outer layer portion 32i. This facilitates the formation of dense inner side margin portions 41i and 42i. As a result, moisture and the like are less likely to penetrate the inner outer layer portion 31i from the outside, thereby achieving high moisture-resistant reliability for the multilayer ceramic capacitor 1.

[0054] Furthermore, the content of Ca-Mn-Si-based oxides in the inner outer layer portion 31i located on the inner layer portion 30 side is preferably 2 Atom% or more and 10 Atom% or less relative to the content of Ca-Mn-Si-based oxides in the outer outer layer portion 31o located on the first main surface 11 side. If the content of Ca-Mn-Si-based oxides in the inner outer layer portion 31i is less than 2 Atom% relative to the content of Ca-Mn-Si-based oxides in the outer outer layer portion 31o located on the first main surface 11 side, the Ca-Mn-Si-based oxides may not be sufficiently contained. If the Ca-Mn-Si-based oxides are not sufficiently contained, many crystals may be formed in the inner outer layer portion 31i. If many crystals are formed in the inner outer layer portion 31i, the area containing the crystals in the inner outer layer portion 31i becomes large, and the area containing Ca-Mn-Si-based oxides in the inner outer layer portion 31i becomes small. That is, the content of Ca-Mn-Si oxides in the inner outer layer portion 31i decreases. While Ca-Mn-Si oxides function as a sintering aid for the inner outer layer portion 31i, a decrease in the content of Ca-Mn-Si oxides in the inner outer layer portion 31i may result in the inner outer layer portion 31i not being sufficiently sintered, potentially making it impossible to ensure the sinterability of the inner outer layer portion 31i. If the sinterability of the inner outer layer portion 31i is not ensured, pores are likely to remain in the region of the inner outer layer portion 31i close to the inner layer portion 30, and moisture or the like may penetrate into the pores in the region of the inner outer layer portion 31i close to the inner layer portion 30 from the outside. As a result, if moisture or the like penetrates into the pores in the region of the inner outer layer portion 31i close to the inner layer portion 30 from the outside, a short circuit may occur, potentially making it impossible to ensure the moisture resistance reliability of the multilayer ceramic capacitor 1. When the content of Ca-Mn-Si-based oxides in the inner outer layer portion 31i is more than 10 Atom % relative to the content of Ca-Mn-Si-based oxides in the outer outer layer portion 31o located on the first main surface 11 side, the area containing the Ca-Mn-Si-based oxides in the inner outer layer portion 31i increases, and the area containing crystals in the inner outer layer portion 31i decreases. In other words, the content of Ca-Mn-Si-based oxides in the inner outer layer portion 31i increases.If the content of Ca-Mn-Si-based oxides in the inner outer layer portion 31i becomes large, a difference in shrinkage behavior during sintering may occur between the inner outer layer portion 31i and the outer outer layer portion 31o. Therefore, due to the difference in shrinkage behavior during sintering between the inner outer layer portion 31i and the outer outer layer portion 31o, cracks may occur between the inner outer layer portion 31i and the outer outer layer portion 31o. As a result, if cracks occur between the inner outer layer portion 31i and the outer outer layer portion 31o and moisture or the like from the outside penetrates through the cracks, short circuits may occur, and the moisture resistance reliability of the multilayer ceramic capacitor 1 may not be ensured.

[0055] In this way, by adjusting the content of Ca-Mn-Si oxide in the inner outer layer portion 31i to 2 Atom % or more and 10 Atom % or less relative to the content of Ca-Mn-Si oxide in the outer outer layer portion 31o located on the first main surface 11 side in the stacking (T) direction of the first outer layer portion 31, it becomes easier to balance the formation of crystals in the inner outer layer portion 31i and the content of the sintering aid. As a result, the sinterability of the inner outer layer portion 31i can be further ensured, a denser inner outer layer portion 31o can be formed, and a multilayer ceramic capacitor 1 with high moisture resistance reliability can be realized.

[0056] Similarly, for the multilayer ceramic capacitor 1 after manufacture, in a WT cross section extending in the stacking (T) direction and width (W) direction of the laminate 10, the content of Ca-Mn-Si-based oxides in the inner outer layer portion 32i located on the inner layer portion 30 side is greater than the content of Ca-Mn-Si-based oxides in the outer outer layer portion 32o located on the second main surface 12 side.

[0057] Furthermore, the content of Ca-Mn-Si-based oxides in the inner outer layer portion 32i located on the inner layer portion 30 side is preferably 2 Atom % or more and 10 Atom % or less relative to the content of Ca-Mn-Si-based oxides in the outer outer layer portion 32o located on the second main surface 12 side. If the content of Ca-Mn-Si-based oxides in the inner outer layer portion 32i is less than 2 Atom % relative to the content of Ca-Mn-Si-based oxides in the outer outer layer portion 32o located on the second main surface 12 side, the Ca-Mn-Si-based oxides may not be sufficiently contained. If the Ca-Mn-Si-based oxides are not sufficiently contained, many crystals may be formed in the inner outer layer portion 32i. If many crystals are formed in the inner outer layer portion 32i, the area containing the crystals in the inner outer layer portion 32i becomes large, and the area containing Ca-Mn-Si-based oxides in the inner outer layer portion 32i becomes small. That is, the content of Ca-Mn-Si oxides in the inner outer layer portion 32i decreases. While Ca-Mn-Si oxides function as a sintering aid for the inner outer layer portion 32i, a decrease in the content of Ca-Mn-Si oxides in the inner outer layer portion 32i may result in the inner outer layer portion 32i not being sufficiently sintered, potentially making it impossible to ensure the sinterability of the inner outer layer portion 32i. This tends to leave pores in the inner outer layer portion 32i near the inner layer portion 30, allowing moisture and other external elements to penetrate into the pores in the inner outer layer portion 32i near the inner layer portion 30. This can result in short circuits, potentially making it impossible to ensure the moisture resistance reliability of the multilayer ceramic capacitor 1. When the content of Ca-Mn-Si-based oxides in the inner outer layer portion 32i is more than 10 Atom % relative to the content of Ca-Mn-Si-based oxides in the outer outer layer portion 32o located on the second main surface 12 side, the area containing Ca-Mn-Si-based oxides in the inner outer layer portion 32i increases, and the area containing crystals in the inner outer layer portion 32i decreases. In other words, the content of Ca-Mn-Si-based oxides in the inner outer layer portion 32i increases. When the content of Ca-Mn-Si-based oxides in the inner outer layer portion 32i increases, differences in shrinkage behavior during sintering may occur between the inner outer layer portion 32i and the outer outer layer portion 32o.Therefore, due to the difference in shrinkage behavior during sintering between the inner outer layer portion 32i and the outer outer layer portion 32o, cracks may occur between the inner outer layer portion 32i and the outer outer layer portion 32o. If cracks occur between the inner outer layer portion 32i and the outer outer layer portion 32o and moisture or the like penetrates through the cracks from the outside, it may not be possible to ensure the moisture resistance reliability of the multilayer ceramic capacitor 1.

[0058] In this way, by adjusting the Ca-Mn-Si oxide content of the inner outer layer portion 32i in the stacking (T) direction of the second outer layer portion 32 to 2 Atom % or more and 10 Atom % or less relative to the Ca-Mn-Si oxide content of the outer outer layer portion 32o located on the second main surface 12 side, it becomes easier to balance the formation of crystals in the inner outer layer portion 32i with the Ca-Mn-Si oxide content. This makes it easier to ensure the sinterability of the inner outer layer portion 32i and form a denser inner outer layer portion 32o. This makes it possible to further improve the moisture resistance reliability of the multilayer ceramic capacitor 1.

[0059] (Specific Method for Measuring Ca-Mn-Si-Based Oxides) The Ca-Mn-Si-based oxide content in the inner outer layer portion 31i and inner outer layer portion 32i located on the inner layer portion 30 side of the laminate 10, and the Ca-Mn-Si-based oxide content in the outer outer layer portion 31o and outer outer layer portion 32o located on the first main surface 11 side or the second main surface 12 side, can be confirmed from the results of images obtained by elemental mapping analysis using WDX. The Ca-Mn-Si-based oxide content in the inner outer layer portion 31i and inner outer layer portion 32i refers to the average value measured at multiple locations in the inner outer layer portion 31i and inner outer layer portion 32i along the stacking (T) direction and at multiple locations in the outer outer layer portion 31o and outer outer layer portion 32o. Specifically, first, a cross-section of the multilayer ceramic capacitor is polished from the first side surface or second side surface to the center of the multilayer ceramic capacitor in the width direction to expose the LT cross section. The polished inner outer layer portion 31i, inner outer layer portion 32i, and outer outer layer portion 31o, outer outer layer portion 32o are then observed by WDX. Observation conditions include a magnification of 3000x and an acceleration voltage of 15 kV, and images of three locations, the left end, right end, and center, of the inner outer layer portion 31i, inner outer layer portion 32i, and outer outer layer portion 31o, outer outer layer portion 32o, are taken with a field of view of 50 μm × 50 μm. Based on the results of the images taken under the above observation conditions and subjected to elemental mapping analysis by WDX, the Ca—Mn—Si-based oxide content of the inner outer layer portion 31i and outer outer layer portion 32i is determined by measuring the Ca—Mn—Si-based oxide content of the left end, right end, and center of the inner outer layer portion 31i, inner outer layer portion 32i and calculating the average value. Similarly, the content of Ca-Mn-Si-based oxides in the outer outer layer portions 31o and 32o can be obtained by measuring the content of Ca-Mn-Si-based oxides in the left end portion, right end portion, and center portion of the outer outer layer portions 31o and 32o and calculating the average value.

[0060] A first side margin 41 and a second side margin 42 are provided to sandwich the inner layer portion 30 in the width (W) direction. The first side margin 41 is located on the first side surface 13 side of the laminate 10, and the second side margin 42 is located on the second side surface 14 side of the laminate 10.

[0061] The first side margin portion 41 can have a two-layer structure laminated in the width (W) direction, and comprises an outer side margin portion 41o located on the first side surface 13 side and an inner side margin portion 41i located closer to the inner layer portion 30 than the outer side margin portion 41o. The thicknesses in the width (W) direction of the outer side margin portion 41o and the inner side margin portion 41i may be approximately the same or different.

[0062] Furthermore, the widthwise thickness of the outer side margin 41o is preferably greater than the widthwise thickness of the inner side margin 41i. Specifically, the widthwise (W) thickness of the outer side margin 41o is preferably 3 μm or greater and 20 μm or less. If the widthwise (W) thickness of the outer side margin 41o is less than 3 μm, the outer side margin 41o may not contain sufficient calcium silicate. If the outer side margin 41o does not contain sufficient calcium silicate, fewer crystals may form within the outer side margin 41o. If fewer crystals form within the outer side margin 41o, the area containing the crystals within the outer side margin 41o becomes smaller, and the area containing the sintering aid within the outer side margin 41o becomes larger. In other words, the amount of sintering aid contained within the outer side margin 41o increases. Because sintering aids are inherently vulnerable to moisture, increasing the content of sintering aid in the outer side margin portion 41o makes the outer side margin portion 41o more vulnerable to moisture. This potentially allows moisture to penetrate the outer side margin portion 41o from the outside. As a result, if moisture penetrates the inner layer portion 30 via the outer side margin portion 41o, a short circuit may occur, potentially reducing the moisture resistance reliability of the multilayer ceramic capacitor 1. When the thickness of the outer side margin portion 41o in the width (W) direction is greater than 20 μm, the outer side margin portion 41o may contain a large amount of calcium silicate. If the outer side margin portion 41o contains a large amount of calcium silicate, a large amount of crystals may form within the outer side margin portion 41o. When a large amount of crystals are formed in the outer side margin portion 41o, the area containing the crystals in the outer side margin portion 41o becomes larger, and the area containing the sintering aid in the outer side margin portion 41o becomes smaller. In other words, the amount of sintering aid contained in the outer side margin portion 41o becomes smaller.If the content of sintering aid in the outer side margin portion 41o is reduced, the outer side margin portion 41o will not be sintered sufficiently, and the sinterability of the outer side margin portion 41o may not be ensured. As a result, pores are likely to remain in the region of the outer side margin portion 41o close to the inner layer portion 30, and moisture or the like may penetrate into the pores in the region of the outer side margin portion 41o close to the inner layer portion 30 from the outside. As a result, if moisture or the like penetrates into the inner layer portion 30 through the pores in the region of the outer side margin portion 41o close to the inner layer portion 30, a short circuit will occur, and the moisture resistance reliability of the multilayer ceramic capacitor 1 may not be ensured.

[0063] Furthermore, the thickness of the inner side margin 41i in the width (W) direction is preferably 2 μm or more and 20 μm or less. If the thickness of the inner side margin 41i in the width (W) direction is less than 2 μm, the inner side margin 41i may not contain sufficient calcium silicate. If the inner side margin 41i does not contain sufficient calcium silicate, crystals may not form in the inner side margin 41i. If crystals are not formed in the inner side margin 41i, the area containing the crystals in the inner side margin 41i becomes smaller, and the area containing the sintering aid in the inner side margin 41i becomes larger. In other words, the content of the sintering aid in the inner side margin 41i increases. Since sintering aids are inherently vulnerable to moisture and the like, if the content of the sintering aid in the inner side margin 41i increases, the inner side margin 41i becomes more vulnerable to moisture and the like. Therefore, moisture or the like may penetrate the inner side margin 41i from the outside. As a result, if moisture or the like penetrates the inner layer portion 30 through the inner side margin 41i, a short circuit may occur, which may reduce the moisture resistance reliability of the multilayer ceramic capacitor 1. If the thickness of the inner side margin 41i in the width (W) direction is greater than 20 μm, the inner side margin 41i may contain a large amount of calcium silicate. If the inner side margin 41i contains a large amount of calcium silicate, many crystals may form within the inner side margin 41i. If many crystals form within the inner side margin 41i, the area containing the crystals within the inner side margin 41i increases, and the area containing the sintering aid within the inner side margin 41i decreases. In other words, the amount of sintering aid contained within the inner side margin 41i decreases. If the content of the sintering aid in the inner side margin portion 41i becomes small, the inner side margin portion 41i will not be sintered sufficiently, and there is a possibility that the sinterability of the inner side margin portion 41i will not be ensured.Therefore, pores are likely to remain in the region of the inner side margin 41i close to the inner layer portion 30, and moisture or the like may penetrate from the outside into the pores in the region of the inner side margin 41i close to the inner layer portion 30. As a result, if moisture or the like penetrates into the inner layer portion 30 through the pores in the region of the inner side margin 41i close to the inner layer portion 30, a short circuit will occur, and the moisture resistance reliability of the multilayer ceramic capacitor 1 may not be ensured.

[0064] Therefore, by setting the thickness in the width (W) direction of the outer side margin portion 41o to be 3 μm or more and 20 μm or less, and the thickness in the width (W) direction of the inner side margin portion 41i to be 2 μm or more and 20 μm or less, a balance is achieved between the crystals formed in the outer side margin portion 41o, the outer side margin portion 42o, the inner side margin portion 41i, and the inner side margin portion 42i and the content of the sintering aid, making it easier to form a denser outer side margin portion 41o. As a result, a dense outer side margin portion 41o is formed while ensuring sinterability, and a multilayer ceramic capacitor 1 with higher moisture resistance reliability can be realized.

[0065] The second side margin portion 42 can have a two-layer structure laminated in the width (W) direction, and comprises an outer side margin portion 42o located on the second side surface 14 side and an inner side margin portion 42i located closer to the inner layer portion 30 than the outer side margin portion 42o. The thicknesses in the width (W) direction of the outer side margin portion 42o and the inner side margin portion 42i may be approximately the same or different.

[0066] Furthermore, the widthwise thickness of the outer side margin 42o is preferably greater than the widthwise thickness of the inner side margin 42i. Specifically, the widthwise (W) thickness of the outer side margin 42o is preferably 3 μm or greater and 20 μm or less. If the widthwise (W) thickness of the outer side margin 42o is less than 3 μm, the outer side margin 42o may not contain sufficient calcium silicate. If the outer side margin 42o does not contain sufficient calcium silicate, fewer crystals may form within the outer side margin 42o. If fewer crystals form within the outer side margin 42o, the area containing the crystals within the outer side margin 42o becomes smaller, and the area containing the sintering aid within the outer side margin 42o becomes larger. In other words, the amount of sintering aid contained within the outer side margin 42o increases. Because sintering aids are inherently vulnerable to moisture, increasing the content of sintering aid in the outer side margin 42o makes the outer side margin 42o more vulnerable to moisture. This potentially allows moisture to penetrate the outer side margin 42o from the outside. As a result, if moisture penetrates the inner layer 30 via the outer side margin 42o, a short circuit may occur, potentially reducing the moisture resistance reliability of the multilayer ceramic capacitor 1. When the thickness of the outer side margin 42o in the width (W) direction is greater than 20 μm, the outer side margin 42o may contain a large amount of calcium silicate. If the outer side margin 42o contains a large amount of calcium silicate, a large amount of crystals may form within the outer side margin 42o. When a large amount of crystals are formed in the outer side margin portion 42o, the area containing the crystals in the outer side margin portion 42o becomes larger, and the area containing the sintering aid in the outer side margin portion 42o becomes smaller. In other words, the amount of sintering aid contained in the outer side margin portion 42o becomes smaller.If the content of sintering aid in the outer side margin portion 42o is reduced, the outer side margin portion 42o will not be sintered sufficiently, and the sinterability of the outer side margin portion 42o may not be ensured. As a result, pores are likely to remain in the region of the outer side margin portion 42o close to the inner layer portion 30, and moisture or the like may penetrate into the pores in the region of the outer side margin portion 42o close to the inner layer portion 30 from the outside. As a result, if moisture or the like penetrates into the inner layer portion 30 through the pores in the region of the outer side margin portion 42o close to the inner layer portion 30, a short circuit will occur, and the moisture resistance reliability of the multilayer ceramic capacitor 1 may not be ensured.

[0067] The thickness of the inner side margin 42i in the width (W) direction is preferably 2 μm or more and 20 μm or less. If the thickness of the inner side margin 42i in the width (W) direction is less than 2 μm, the inner side margin 42i may not contain enough calcium silicate. If the inner side margin 42i does not contain enough calcium silicate, few crystals may form within the inner side margin 42i. If few crystals form within the inner side margin 42i, the area containing the crystals within the inner side margin 42i becomes smaller, and the area containing the sintering aid within the inner side margin 42i becomes larger. In other words, the content of the sintering aid within the inner side margin 42i increases. Since sintering aids are inherently vulnerable to moisture and other factors, if the content of the sintering aid within the inner side margin 42i increases, the inner side margin 42i becomes more vulnerable to moisture and other factors. Therefore, moisture or the like may penetrate the inner side margin 42i from the outside. As a result, if moisture or the like penetrates the inner layer portion 30 through the inner side margin 42i, a short circuit may occur, which may reduce the moisture resistance reliability of the multilayer ceramic capacitor 1. If the thickness of the inner side margin 42i in the width (W) direction is greater than 20 μm, the inner side margin 42i may contain a large amount of calcium silicate. If the inner side margin 42i contains a large amount of calcium silicate, many crystals may form within the inner side margin 42i. If many crystals form within the inner side margin 42i, the area containing the crystals within the inner side margin 42i increases, and the area containing the sintering aid within the inner side margin 42i decreases. In other words, the amount of sintering aid contained within the inner side margin 42i decreases. If the content of the sintering aid in the inner side margin portion 42i becomes small, the inner side margin portion 42i will not be sintered sufficiently, and there is a possibility that the sinterability of the inner side margin portion 42i will not be ensured.Therefore, pores are likely to remain in the region of the inner side margin 42i close to the inner layer portion 30, and moisture or the like may penetrate from the outside into the pores in the region of the inner side margin 42i close to the inner layer portion 30. As a result, if moisture or the like penetrates into the inner layer portion 30 through the pores in the region of the inner side margin 42i close to the inner layer portion 30, a short circuit will occur, and the moisture resistance reliability of the multilayer ceramic capacitor 1 may not be ensured.

[0068] Therefore, by setting the thickness in the width (W) direction of the outer side margin portion 42o to be 3 μm or more and 20 μm or less, and the thickness in the width (W) direction of the inner side margin portion 42i to be 2 μm or more and 20 μm or less, a balance is achieved between the crystals formed in the outer side margin portion 42o, the outer side margin portion 42o, the inner side margin portion 42i, and the inner side margin portion 42i, and the content of the sintering aid, making it easier to form a denser outer side margin portion 42o. As a result, a dense outer side margin portion 42o is formed while ensuring sinterability, and a multilayer ceramic capacitor 1 with higher moisture resistance reliability can be realized.

[0069] The dielectric layers forming the first side margin portion 41 and the second side margin portion 42 are made of a dielectric ceramic containing a perovskite compound containing Ca and Zr. Such a dielectric ceramic is CaCO ３ , SrCO ３ , BaCO ３ , TiO ２ , ZrO ２ The powder obtained by mixing powders such as these, calcining the mixture, and then pulverizing the mixture can be used as the main ceramic raw material. The main ceramic raw material may contain sintering aids such as Ca, Mn, Si, and SiO ２ , MnCO ３ The following may be added, but is not limited to these.

[0070] The calcium silicate content in the outer side margins 41o and 42o located on the first side surface 13 or second side surface 14 of the laminate 10 is higher than the calcium silicate content in the inner side margins 41i and 42i located on the inner layer portion 30 side. By adjusting the calcium silicate content in the width (W) direction of the first side margin 41 and the second side margin 42 in this way, the calcium silicate content in the outer side margins 41o and 42o is likely to be higher than that in the inner side margins 41i and 42i. This achieves a balance between the crystals formed in the outer side margins 41o and 42o and the content of the sintering aid, making it easier to form denser outer side margins 41o and 42o. As a result, denser side margin portions 41o and outer side margin portions 42o are formed while ensuring sinterability, and a multilayer ceramic capacitor 1 with high moisture resistance reliability can be realized.

[0071] Furthermore, the content of Ca—Mn—Si-based oxides in the inner side margins 41i and 42i located on the inner layer portion 30 side is greater than the content of Ca—Mn—Si-based oxides in the outer side margins 41o and 42o located on the first side surface 13 or second side surface 14 side of the laminate 10. Adjusting the content of Ca—Mn—Si-based oxides in the width (W) direction of the first side margin 41 and the second side margin 42 thus facilitates the inclusion of large amounts of Ca—Mn—Si-based oxides in the inner side margins 41i and 42i. The Ca—Mn—Si-based oxides function as a sintering aid during firing, ensuring the sinterability of the inner side margins 41i and 42i. This facilitates the formation of dense inner side margins 41i and 42i. As a result, moisture and the like are less likely to penetrate into the inner outer layer portion 31i from the outside, and the moisture resistance reliability of the multilayer ceramic capacitor 1 can be improved.

[0072] Furthermore, the content of Ca—Mn—Si-based oxides in the inner side margins 41i and 42i located on the inner layer portion 30 side is preferably 2 Atom % or more and 10 Atom % or less relative to the content of Ca—Mn—Si-based oxides in the outer side margins 41o and 42o located on the first side face 13 or second side face 14 side of the laminate 10. If the content of Ca—Mn—Si-based oxides in the inner side margins 41i and 42i is less than 2 Atom % relative to the content of Ca—Mn—Si-based oxides in the outer side margins 41o and 42o located on the first side face 13 or second side face 14 side, there is a possibility that the Ca—Mn—Si-based oxides are not sufficiently contained. If the Ca-Mn-Si-based oxides are not sufficiently contained, a large number of crystals may be formed in the inner side margin portions 41i and 42i. If a large number of crystals are formed in the inner side margin portions 41i and 42i, the area containing the crystals in the inner side margin portions 41i and 42i increases, and the area containing the Ca-Mn-Si-based oxides in the inner side margin portions 41i and 42i decreases. In other words, the content of Ca-Mn-Si-based oxides in the inner side margin portions 41i and 42i decreases. Although Ca—Mn—Si-based oxides function as sintering aids for the inner side margin portions 41i and 42i, if the content of Ca—Mn—Si-based oxides in the inner side margin portions 41i and 42i becomes small, the inner side margin portions 41i and 42i will not be sintered sufficiently, and it may be impossible to ensure the sinterability of the inner side margin portions 41i and 42i. If the sinterability of the inner side margin portions 41i and 42i cannot be ensured, pores are likely to remain in the regions of the inner side margin portions 41i and 42i close to the inner layer portion 30, and moisture and the like may penetrate from the outside into the pores in the regions of the inner side margin portions 41i and 42i close to the inner layer portion 30.As a result, if moisture or the like from the outside penetrates into the pores in the regions of the inner side margin portions 41i and 42i near the inner layer portion 30, a short circuit may occur, and the moisture resistance reliability of the multilayer ceramic capacitor 1 may not be ensured. If the content of Ca-Mn-Si-based oxides in the inner side margin portions 41i and 41i is more than 10 Atom % relative to the content of Ca-Mn-Si-based oxides in the outer side margin portions 41o and 42o located on the first side surface 13 side, the area containing Ca-Mn-Si-based oxides in the inner side margin portions 41i and 42i becomes larger, and the area containing crystals in the inner side margin portions 41i and 42i becomes smaller. In other words, the content of Ca-Mn-Si-based oxides in the inner side margin portions 41i becomes larger. If the content of Ca—Mn—Si-based oxides in the inner side margin 41i and the inner side margin 42i becomes large, differences in shrinkage behavior during sintering may occur between the inner side margin 41i and the outer side margin 41o, and between the inner side margin 42i and the outer side margin 42o. Therefore, due to differences in shrinkage behavior during sintering between the inner side margin 41i, the inner side margin 42i and the outer side margin 41o, and the outer side margin 42o, cracks may occur between the inner side margin 41i and the outer side margin 41o, and between the inner side margin 42i and the outer side margin 42o. As a result, cracks occur between the inner side margin portion 41i and the outer side margin portion 41o, and between the inner side margin portion 42i and the outer side margin portion 42o. If moisture or the like from the outside penetrates through the cracks, a short circuit may occur, and the moisture resistance reliability of the multilayer ceramic capacitor 1 may not be ensured.

[0073] In this way, by adjusting the content of Ca—Mn—Si-based oxide in the inner side margin portion 41i and the inner side margin portion 42i in the width (W) direction of the first side margin portion 41 and the second side margin portion 42 to 2 Atom % or more and 10 Atom % or less relative to the content of Ca—Mn—Si-based oxide in the outer side margin portion 41o and the outer side margin portion 42o located on the first side surface 13 and the second side surface 14 sides, respectively, it becomes easier to balance the formation of crystals in the inner side margin portion 41i and the inner side margin portion 42i with the content of the sintering aid. This makes it possible to further ensure the sinterability of the inner side margin portion 41i and the inner side margin portion 42i, form a denser inner side margin portion 41i, and realize a multilayer ceramic capacitor 1 with high moisture-resistant reliability.

[0074] Although the two-layer structure of the first side margin 41 and the second side margin 42 can be observed in a dark field using an optical microscope due to differences in sinterability, depending on the sintering conditions, the outer side margin 41o and the inner side margin 41i, or the outer side margin 42o and the inner side margin 42i, may become one after firing, making it difficult to recognize the boundary surface. Also, as long as the calcium silicate content can be adjusted in the width (W) direction, it is not necessary for the first side margin 41 and the second side margin 42 to each have a two-layer structure. That is, in the WT cross section of the laminate 10 extending in the stacking (T) direction and the width (W) direction, the calcium silicate content in the outer side margin 41o located on the first side surface 13 side is greater than the calcium silicate content in the inner side margin 41i located on the inner layer portion 30 side, and the calcium silicate content in the outer side margin 42o located on the second side surface 14 side is greater than the calcium silicate content in the inner side margin 42i located on the inner layer portion 30 side. Therefore, the crystals formed in the outer side margin 41o and the outer side margin 42o are balanced with the content of the sintering aid, facilitating the formation of dense outer side margin 41o and outer side margin 42o. As a result, dense outer side margin 41o and outer side margin 42o are formed while ensuring sinterability, thereby realizing a multilayer ceramic capacitor 1 with high moisture resistance reliability.

[0075] (Method for Measuring the Width (W) Direction Thickness of the Outer Side Margin 41o, the Outer Side Margin 42o, the Inner Side Margin 41i, and the Inner Side Margin 42i) The method for measuring the width (W) direction thickness of the outer side margin 41o, the outer side margin 42o, the inner side margin 41i, and the inner side margin 42i can be confirmed from the results of WDX. Specifically, cross-section polishing is first performed from the first end face or the second end face of the multilayer ceramic capacitor to the center in the longitudinal direction of the multilayer ceramic capacitor to expose the WT cross section. Then, the first side margin 41 and the second side margin 42 are observed by WDX. The conditions for observation are a magnification of 2000x and an accelerating voltage of 15 kV. Images are taken of three locations in the width (W) direction of the first side margin 41 and the second side margin 42: the left end, the right end, and the center, with a field of view of 50 μm × 50 μm. Based on the results of imaging under the above observation conditions and elemental mapping analysis using WDX, the thickness of the outer side margin 41o in the width (W) direction was determined by measuring the locations containing the most calcium silicate from the first side surface 13 and the second side surface 14 of the upper, lower, and central portions of the first side margin 41 and the second side margin 42 toward the inner layer portion 30 in the stacking (T) direction using the scale in the image data obtained by elemental mapping analysis, and calculating the average value. The thickness of the inner side margin 41i in the width (W) direction was determined by measuring the distance from the portion of the outer side margin 41i closest to the inner layer portion 30 in the width (W) direction to the side surface of the inner layer portion 30 in the width (W) direction using the scale in the image data obtained by elemental mapping analysis, and calculating the average value for each of the upper, lower, and central portions. The thicknesses of the inner side margin portion 42i and the outer side margin portion 42o can also be confirmed by the same measurement method.

[0076] (Specific Method for Measuring Calcium Silicate in Side Margins) The calcium silicate content in the inner side margins 41i and 42i located on the inner layer portion 30 side and the calcium silicate content in the outer side margins 41o and 42o located on the first side surface 13 or second side surface 14 side of the laminate 10 can be confirmed from the results of images obtained by elemental mapping analysis using WDX. The calcium silicate content in the inner side margins 41i and 42i refers to the average value of measurements taken at multiple locations on the inner side margin 41i and multiple locations on the outer side margins 41o and 42o along the stacking (T) direction. Specifically, first, the multilayer ceramic capacitor is cross-sectionally polished from the first end face or second end face to the center of the multilayer ceramic capacitor in the longitudinal direction to expose the WT cross section. The inner side margins 41i, 42i, and the outer side margins 41o, 42o are then observed by WDX. The conditions for observation are a magnification of 2000x and an acceleration voltage of 15 kV. Images are taken of the upper, lower, and central portions of the inner side margins 41i, 42i, and the outer side margins 41o, 42o along the stacking (T) direction with a field of view of 50 μm × 50 μm. Based on the results of elemental mapping analysis using WDX on images captured under the above observation conditions, the calcium silicate content of the inner side margins 41i, 42i is determined by measuring the calcium silicate content of the upper, lower, and central portions of the inner side margins 41i, 42i along the stacking (T) direction and calculating the average value. The calcium silicate content of the outer side margin portions 41o and 42o is obtained by taking images based on the above observation conditions, measuring the calcium silicate content of the upper, lower, and central portions along the stacking (T) direction of the outer side margin portions 41o and 42o, and calculating the average value.

[0077] (Specific Method for Measuring Ca-Mn-Si-Based Oxides in Side Margins) The Ca-Mn-Si-based oxide content in the inner side margins 41i and 42i located on the inner layer portion 30 side and the Ca-Mn-Si-based oxide content in the outer side margins 41o and 42o located on the first side surface 13 or second side surface 14 side of the laminate 10 can be confirmed from the results of images obtained by elemental mapping analysis using WDX. The Ca-Mn-Si-based oxide content in the inner side margins 41i and 42i represents the average value of measurements taken at multiple locations on the inner side margin 41i and multiple locations on the outer side margins 41o and 42o along the stacking (T) direction. Specifically, first, the multilayer ceramic capacitor is cross-sectionally polished from the first end face or second end face to the center of the multilayer ceramic capacitor in the longitudinal direction to expose the WT cross section. The inner side margin 41i, the inner side margin 42i, and the outer side margin 41o, the outer side margin 42o are then observed by WDX. The conditions for observation are a magnification of 2000x and an acceleration voltage of 15 kV, and images are taken of the upper, lower, and central portions of the inner side margin 41i, the inner side margin 42i, the outer side margin 41o, and the outer side margin 42o along the stacking (T) direction with a field of view of 50 μm × 50 μm. From the results of the images taken under the above observation conditions and subjected to elemental mapping analysis by WDX, the Ca—Mn—Si-based oxide content of the inner side margin 41i, the inner side margin 42i is determined by measuring the Ca—Mn—Si-based oxide content of the upper, lower, and central portions along the stacking (T) direction of the inner side margin 41i, the inner side margin 42i and the inner side margin 42i and calculating the average value. The Ca-Mn-Si-based oxide content of the outer side margin portions 41o and 42o is obtained by measuring the Ca-Mn-Si-based oxide content of the upper, lower, and central portions along the stacking (T) direction of the outer side margin portions 41o and 42o and calculating the average value.Images were taken under the above observation conditions and subjected to elemental mapping analysis using WDX, and the results of the images confirmed the content of Ca-Mn-Si-based oxides in the inner side margin portions 41i, 42i and the outer side margin portions 41o, 42o.

[0078] A method for manufacturing the multilayer ceramic capacitor 1 (first embodiment) will now be described.

[0079] Ceramic green sheets to become the dielectric layer 20, the first outer layer portion 31, the second outer layer portion 32, the first side margin portion 41, and the second side margin portion 42 are prepared.

[0080] The ceramic green sheets forming the dielectric layers are made of a dielectric ceramic containing a perovskite-type compound containing Ca and Zr. Such a dielectric ceramic is CaCO ３ , SrCO ３ , BaCO ３ , TiO ２ , ZrO ２ The powder obtained by mixing powders such as SiO and the like, calcining the mixture, and then pulverizing the mixture can be used as the main ceramic raw material. ２ , MnCO ３ The ceramic green sheet contains the above ceramic raw materials as well as binders and solvents. The ceramic raw materials may also contain additives containing rare earth elements. By changing the elements contained in the additives, the composition of the dielectric forming each part can be changed. It is preferable that the ceramic raw materials, which are the main components, are the same. The ceramic green sheet is formed, for example, on a carrier film using a die coater, gravure coater, microgravure coater, etc.

[0081] The dielectric layers of the inner outer layer portions 31i, 32i and the outer outer layer portions 31o, 32o that form a two-layer structure in the first outer layer portion 31 and the second outer layer portion 32 are made of a dielectric ceramic containing a perovskite-type compound containing Ca and Zr. ３ , SrCO ３ , BaCO ３ , TiO２ , ZrO ２ The powder obtained by mixing powders such as SiO and the like, calcining the mixture, and then pulverizing the mixture can be used as the main ceramic raw material. ２ , MnCO ３ The ceramic green sheets forming the inner outer layer portions 31i and 32i may contain more MnCO than the ceramic green sheets forming the outer outer layer portions 31o and 32o. ３ The ceramic green sheets forming the outer outer layer portion 31o and the outer outer layer portion 32o contain a larger amount of SiO than the ceramic green sheets forming the inner outer layer portion 31i and the inner outer layer portion 32i. ２ The amount of glass added is increased.

[0082] As a result, in the manufactured multilayer ceramic capacitor 1, the calcium silicate content in the outer outer layer portions 31o and 32o is greater than the calcium silicate content in the inner outer layer portions 31i and 32i located on the inner layer portion 30 side. Also, the Ca—Mn—Si-based oxide content in the inner outer layer portions 31i and 32i located on the inner layer portion 30 side is greater than the Ca—Mn—Si-based oxide content in the outer outer layer portions 31o and 32o. By adjusting the contents of calcium silicate and Ca—Mn—Si-based oxide in the stacking (T) direction of the first outer layer portion 31 or the stacking (T) direction of the second outer layer portion 32 in this manner, dense outer outer layer portions 31o, 32o, inner outer layer portions 31i, and inner outer layer portions 32i are formed while ensuring sinterability, and a multilayer ceramic capacitor 1 with high moisture resistance reliability can be realized.

[0083] 6, 7, and 8 are plan views schematically showing examples of ceramic green sheets, each showing a first ceramic green sheet 101 for forming the inner layer portion 30, a second ceramic green sheet 102 for forming the inner layer portion 30, and a third ceramic green sheet 103 for forming the first outer layer portion 31 and the second outer layer portion 32, respectively.

[0084] Cutting lines X and Y are marked on the first ceramic green sheet 101, the second ceramic green sheet 102, and the third ceramic green sheet 103 for cutting into individual multilayer ceramic capacitors 1. The cutting line X is parallel to the length (L) direction, and the cutting line Y is parallel to the width (W) direction.

[0085] As shown in FIG. 6, in the first ceramic green sheet 101, an unfired first internal electrode layer 121a corresponding to the first internal electrode layer 21a is formed on an unfired dielectric layer 120 corresponding to the dielectric layer 20.

[0086] As shown in FIG. 7, in the second ceramic green sheet 102, an unfired second internal electrode layer 121b corresponding to the second internal electrode layer 21b is formed on an unfired dielectric layer 120 corresponding to the dielectric layer 20.

[0087] The method for producing the first ceramic green sheet 101 shown in FIG. 6 and the second ceramic green sheet 102 shown in FIG. 7 is not particularly limited, but an example is a method in which a conductive paste that will become the first internal electrode layer 21 a or the second internal electrode layer 21 b by firing is applied to a predetermined region on the surface of the unfired dielectric layer 120.

[0088] 8, the third ceramic green sheets 103 for forming the first outer layer portions 31 and the second outer layer portions 32 do not have unsintered first internal electrode layers 121a and second internal electrode layers 121b formed thereon, unlike the first ceramic green sheets 101 and the second ceramic green sheets 102. There are two types of third ceramic green sheets 103, the ceramic green sheets for forming the inner outer layer portions 31i, 32i and the ceramic green sheets for forming the outer outer layer portions 31o, 32o, which have different component compositions.

[0089] The unfired first internal electrode layer 121 a and the second internal electrode layer 121 b can be formed using any conductive paste. For forming the first internal electrode layer 121 a and the second internal electrode layer 121 b using the conductive paste, for example, a screen printing method, a gravure printing method, or the like can be used.

[0090] The unsintered first internal electrode layer 121a and second internal electrode layer 121b are arranged across two adjacent regions in the length (L) direction separated by a cutting line Y, have a predetermined width in the width (W) direction, and extend in a strip shape in the length (L) direction. In the first internal electrode layer 121a and the second internal electrode layer 121b, the regions separated by the cutting line Y are shifted by one row in the length (L) direction. In other words, the cutting line Y passing through the center of the first internal electrode layer 121a passes through the region between the adjacent second internal electrode layers 121b, and the cutting line Y passing through the center of the second internal electrode layer 121b passes through the region between the adjacent first internal electrode layers 121a.

[0091] A mother block is produced by stacking the first ceramic green sheet 101 and the second ceramic green sheet 102, and stacking third ceramic green sheets to form the inner outer layer portion 31i, the inner outer layer portion 32i, the outer outer layer portion 31o, and the outer outer layer portion 32o, respectively.

[0092] Fig. 9 is an exploded perspective view showing an example of a mother block. For ease of explanation, Fig. 9 shows an exploded view of a first ceramic green sheet 101, a second ceramic green sheet 102, and a third ceramic green sheet 103. In an actual mother block 104, the first ceramic green sheet 101, the second ceramic green sheet 102, and the third ceramic green sheet 103 are pressure-bonded together by means of a hydrostatic press or the like.

[0093] 9, first ceramic green sheets 101 and second ceramic green sheets 102 corresponding to the inner layer portion 30 are alternately stacked in the stacking (T) direction. Furthermore, third ceramic green sheets 103 corresponding to the inner outer layer portion 31i, inner outer layer portion 32i and outer outer layer portion 31o, outer outer layer portion 32o are stacked on the top and bottom surfaces in the stacking (T) direction of the alternately stacked first ceramic green sheets 101 and second ceramic green sheets 102, respectively.

[0094] The mother block 104 thus obtained is cut along cutting lines X and Y (see FIGS. 6, 7, and 8) to produce a plurality of green chips. For this cutting, methods such as dicing, press cutting, and laser cutting are used.

[0095] Fig. 10 is a perspective view schematically illustrating an example of a green chip. The green chip 110 shown in Fig. 10 has a laminated structure formed of a plurality of unfired dielectric layers 120, first internal electrode layers 121a, and second internal electrode layers 121b. The first side surface 113 and the second side surface 114 of the green chip 110 are surfaces revealed by cutting along the cutting line X, and the first end surface 115 and the second end surface 116 are surfaces revealed by cutting along the cutting line Y. The first side surface 113 and the second side surface 114 expose the first internal electrode layer 121a and the second internal electrode layer 121b. Furthermore, the first internal electrode layer 121a is exposed at the first end surface 115, and the second internal electrode layer 121b is exposed at the second end surface 116.

[0096] When cutting the mother block 104 to obtain multiple green chips 110, the first side surface 113 and the second side surface 114 of the green chip 110 may be slightly plastically deformed downward due to stress applied to the cutting direction (the downward direction in the figure). Furthermore, the cut surface may not be sufficiently smooth, or foreign matter may be present on the cut surface. Therefore, it is preferable to polish the first side surface 113 and the second side surface 114 to remove the deformed portions.

[0097] An unsintered laminate is produced by forming unsintered side margin portions on the first side surface 113 and the second side surface 114 of the obtained green chip 110. The unsintered side margin portions are formed, for example, by attaching ceramic green sheets made of a dielectric ceramic to the first side surface 113 and the second side surface 114 of the green chip.

[0098] The ceramic green sheets of the inner side margin portion 41i, the inner side margin portion 42i, the outer side margin portion 41o, and the outer side margin portion 42o, which respectively constitute the first side margin portion 41 and the second side margin portion 42, are made of a dielectric ceramic containing a perovskite-type compound containing Ca and Zr. Such a dielectric ceramic is CaCO ３ , SrCO ３ , BaCO ３ , TiO ２ , ZrO ２ The powder obtained by mixing powders such as SiO and the like, calcining the mixture, and then pulverizing the mixture can be used as the main ceramic raw material. ２ , MnCO ３ The ceramic green sheets forming the inner side margin portions 41i and 42i contain less MnCO than the ceramic green sheets forming the outer side margin portions 41o and 42o. ３ The ceramic green sheets forming the outer side margin portions 41 o and 42 o contain a larger amount of SiO than the ceramic green sheets forming the inner side margin portions 41 i and 42 i. ２ The amount of glass added is increased.

[0099] As a result, in the manufactured multilayer ceramic capacitor 1, the calcium silicate content in the outer side margin portions 41o, 42o is greater than the calcium silicate content in the inner side margin portions 41i, 42i located on the inner layer portion 30 side. Also, the Ca-Mn-Si-based oxide content in the inner side margin portions 41i, 42i located on the inner layer portion 30 side is greater than the Ca-Mn-Si-based oxide content in the outer side margin portions 41o, 42o. By adjusting the calcium silicate and Ca-Mn-Si-based oxide contents in the width (W) direction of the first side margin portion 41 and the second side margin portion 42 in this way, dense ceramic layers are formed while ensuring sinterability, and a multilayer ceramic capacitor 1 with high moisture-resistant reliability can be realized.

[0100] An unsintered first side margin 41 is formed by pressing and punching a ceramic green sheet corresponding to the inner side margin 41i and then a ceramic green sheet corresponding to the outer side margin 41o against the first side surface 113 of the green chip 110. An unsintered second side margin 42 is formed by pressing and punching a ceramic green sheet corresponding to the inner side margin 42i and then a ceramic green sheet corresponding to the outer side margin 42o against the second side surface 114 of the green chip 110. In this manner, an unsintered laminate is obtained.

[0101] In this way, in the laminate 10 formed by attaching the inner side margin portion 41i, the inner side margin portion 42i and the outer side margin portion 41o, the outer side margin portion 42o to the green chip 110, the ends of one side in the width (W) direction of the multiple internal electrode layers 21 can be aligned in the stacking (T) direction, and when viewing the WT cross section of the laminate 10 extending in the stacking (T) direction and the width (W) direction, the misalignment in the width (W) direction of all adjacent internal electrode layers 21 can be made 5 μm or less.

[0102] (Method for measuring the amount of misalignment in the width (W) direction of the width direction ends of all adjacent internal electrode layers 21) The amount of misalignment in the width (W) direction of the width direction ends of all adjacent internal electrode layers 21 can be measured using a scanning electron microscope (hereinafter referred to as SEM). Specifically, first, cross-section polishing is performed from the first end face or the second end face of the multilayer ceramic capacitor to the center in the longitudinal direction of the multilayer ceramic capacitor to expose the WT cross section. Next, the WT cross section is observed using an SEM. The observation conditions are a magnification of 2000 times and an acceleration voltage of 5 kV, and the width direction ends of the internal electrode layers 21 are imaged at the top, bottom, and center along the lamination (T) direction with a field of view of 50 μm × 50 μm. Images are taken based on the above observation conditions, and the distance between the ends of adjacent internal electrode layers 21 in the width (W) direction is measured using the scale in the SEM image, thereby confirming the amount of misalignment in the width (W) direction of all adjacent internal electrode layers 21.

[0103] In this way, by aligning one end of the plurality of internal electrode layers 21 in the width (W) direction in the lamination (T) direction, it becomes possible to accurately set the capacitance of the multilayer ceramic capacitor. Also, because the side edges of the internal electrode layers 21 in the width (W) direction extend linearly in the length (L) direction, the current path flowing on the surface becomes short, the equivalent series inductance (ESL) can be suppressed, and it becomes possible to prevent short circuits between adjacent internal electrode layers, thereby realizing a multilayer ceramic capacitor 1 with high reliability.

[0104] In the above embodiment, an example is shown in which ceramic green sheets corresponding to the inner side margin portion 41i and the inner side margin portion 42i and ceramic green sheets corresponding to the outer side margin portion 41o and the outer side margin portion 42o are pressed against the first side surface 113 and the second side surface 114 of the green chip 110, respectively, and then punched out. However, this is not limited to this, and for example, an unsintered laminate can also be obtained by applying ceramic paste to form the inner side margin portion 41i and the inner side margin portion 42i, respectively, to the first side surface 113 and the second side surface 114 of the green chip 110, and then further applying ceramic paste to form the outer side margin portion 41o and the outer side margin portion 42o.

[0105] The green laminate obtained by the above method is preferably subjected to barrel polishing, etc. By polishing the green laminate, the corners and ridges of the laminate 10 after firing are rounded.

[0106] A first external electrode 51a and a second external electrode 52 are formed on the first end surface 15 and the second end surface 16 of the laminate 10, respectively. The first external electrode 51 and the second external electrode 52 can be formed, for example, by a base electrode layer and a plating layer disposed on the base electrode layer. The base electrode layer is formed by applying a conductive paste containing a metal component and a glass component to the first end surface 15 and the second end surface 16 of the laminate 10 and then baking the paste. Examples of the metal component contained in the conductive paste include metals such as Cu, Ni, Ag, Pd, and Au, and alloys of Ag and Pd. Examples of the glass component contained in the conductive paste include B-Si glass, Ba-B-Si glass, B-Si-Zn glass, B-Si-Zn-Ba glass, and B-Si-Zn-Ba-Ca-Al glass.

[0107] The plating layer disposed on the base electrode layer includes at least one of metals such as Cu, Ni, Ag, Pd, and Au, or an alloy of Ag and Pd. The plating layer may have a two-layer structure of, for example, a Ni plating layer and a Sn plating layer. However, the plating layer may be a single layer or multiple layers.

[0108] In this manner, the multilayer ceramic capacitor 1 is manufactured.

[0109] In the above embodiment, the mother block 104 is cut along the cutting lines X and Y to obtain a plurality of green chips 110, and then unfired side margin portions are formed on both sides of the green chips 110. However, the following modifications are also possible.

[0110] That is, by cutting the mother block only along the cutting lines X, a plurality of rod-shaped green block bodies are obtained in which the first internal electrode layers and the second internal electrode layers are exposed on the side surfaces that appear by cutting along the cutting lines X, and then unsintered side margin portions are formed on both side surfaces of the green block body, followed by cutting along the cutting lines Y to obtain a plurality of unsintered laminate bodies, and then the unsintered laminate bodies may be fired. After firing, a multilayer ceramic capacitor can be manufactured by performing the same steps as in the above-described embodiment.

[0111] Next, a description will be given of another method (second embodiment) for manufacturing the multilayer ceramic capacitor 1. The second embodiment will be described mainly focusing on the differences from the first embodiment.

[0112] 11 and 12 show a first ceramic green sheet 101 and a second ceramic green sheet 102 for forming the inner layer portion 30, respectively. These correspond to the first ceramic green sheet 101 in FIG. 6 and the second ceramic green sheet 102 in FIG. 7 in the first embodiment. The third ceramic green sheet 103 used in the second embodiment has the same form as the third ceramic green sheet 103 used in the first embodiment shown in FIG. 8. The third ceramic green sheet 103 used in the second embodiment is made of MnCO 3 as in the first embodiment. ３and a layer for forming the inner and outer layer portions 31i and 32i containing a relatively large amount of Mn compounds such as SiO. ２ Two types of glass are prepared, one for forming the outer layer portions 31o and 32o, and the other for forming the outer layer portions 31o and 32o, which contain a relatively large amount of glass.

[0113] The first ceramic green sheet 101, the second ceramic green sheet 102, and the third ceramic green sheet 103 are shown with cutting lines X and Y for cutting into individual multilayer ceramic capacitors 1. The cutting line X is parallel to the length (L) direction, and the cutting line Y is parallel to the width (W) direction.

[0114] As shown in Fig. 11 , in the first ceramic green sheet 101, an unsintered first internal electrode layer 121a corresponding to the first internal electrode layer 21a is formed on an unsintered dielectric layer 120 corresponding to the dielectric layer 20. In the first ceramic green sheet 101 shown in Fig. 11 , ceramic pastes 141i and 142i are applied continuously in the length (L) direction to both sides of the first internal electrode layer 121a in the width (W) direction, and ceramic pastes 141o and 142o are further applied continuously in the length (L) direction to both sides thereof. In the embodiment shown in Fig. 11 , the first ceramic green sheet 101 is cut along the cutting line X, so that the ceramic pastes 141o and 142o having the same component composition can be applied at once to the unsintered dielectric layer 120.

[0115] As shown in Fig. 12, in the second ceramic green sheet 102, an unsintered second internal electrode layer 121b corresponding to the second internal electrode layer 21b is formed on an unsintered dielectric layer 120 corresponding to the dielectric layer 20. In the second ceramic green sheet 102 shown in Fig. 12, ceramic pastes 141i and 142i are applied continuously in the length (L) direction to both sides of the width (W) direction of the second internal electrode layer 121b, and ceramic pastes 141o and 142o are further applied continuously in the length (L) direction to both sides thereof. In the embodiment shown in Fig. 12, the second ceramic green sheet 102 is cut along the cutting line X, so that the ceramic pastes 141o and 142o having the same component composition can be applied at once to the unsintered dielectric layer 120.

[0116] The ceramic pastes 141i, 142i, 141o, and 142o are made of a dielectric ceramic containing a perovskite-type compound containing Ca and Zr. Such a dielectric ceramic is CaCO ３ , SrCO ３ , BaCO ３ , TiO ２ , ZrO ２ The powder obtained by mixing powders such as SiO and the like, calcining the mixture, and then pulverizing the mixture can be used as the main ceramic raw material. ２ , MnCO ３ The inner ceramic pastes 141i and 142i applied to both sides of the first internal electrode layer 21a or the second internal electrode layer 21b have a higher MnCO content than the outer ceramic pastes 141o and 142o applied to both sides thereof. ３ The amount of Mn compounds added is increased. The outer ceramic pastes 141o and 142o contain more SiO than the inner ceramic pastes 141i and 142i. ２ The amount of glass added is increased.

[0117] The first internal electrode layer 121 a and the second internal electrode layer 121 b can be formed using any conductive paste. For forming the first internal electrode layer 121 a and the second internal electrode layer 121 b using the conductive paste, for example, a screen printing method, a gravure printing method, or the like can be used.

[0118] The unsintered first internal electrode layer 121a and second internal electrode layer 121b are arranged across two adjacent regions in the length (L) direction separated by a cutting line Y, have a predetermined width in the width (W) direction, and extend in a strip shape in the length (L) direction. In the first internal electrode layer 121a and the second internal electrode layer 121b, the regions separated by the cutting line Y are shifted by one row in the length (L) direction. In other words, the cutting line Y passing through the center of the first internal electrode layer 121a passes through the region between the adjacent second internal electrode layers 121b, and the cutting line Y passing through the center of the second internal electrode layer 121b passes through the region between the adjacent first internal electrode layers 121a.

[0119] The first ceramic green sheet 101 and the second ceramic green sheet 102 are laminated together, and third ceramic green sheets forming the inner outer layer portions 31i, 32i and the outer outer layer portions 31o, 32o are laminated together, followed by cutting along cutting lines X and Y (see FIGS. 11, 12, and 8) to produce green chips. In the second embodiment, it is not necessary to attach ceramic green sheets for forming side margin portions to both side surfaces of the green chip, as in the first embodiment.

[0120] In the multilayer ceramic capacitor 1 of the second embodiment obtained by firing the green chip, similar to the multilayer ceramic capacitor of the first embodiment, in a WT cross section extending in the stacking (T) direction and width (W) direction of the laminate 10, the calcium silicate content in the outer side margin 41o located on the first side surface 13 side is higher than the calcium silicate content in the inner side margin 41i located on the inner layer portion 30 side. Furthermore, the calcium silicate content in the outer side margin 42o located on the second side surface 14 side is higher than the calcium silicate content in the inner side margin 42i located on the inner layer portion 30 side. Therefore, the crystals formed in the outer side margin 41o and the outer side margin 42o and the content of the sintering aid are balanced, making it easier to form a denser outer side margin 41o. As a result, dense ceramic layers are formed while ensuring sinterability, resulting in a multilayer ceramic capacitor 1 with high moisture resistance reliability.

[0121] Similarly, in the manufactured multilayer ceramic capacitor 1, in a WT cross section extending in the stacking (T) direction and width (W) direction of the laminate 10, the content of Ca-Mn-Si-based oxides in the inner side margin 41i located on the inner layer portion 30 side is greater than the content of Ca-Mn-Si-based oxides in the outer side margin 41o located on the first side surface 13 side. Furthermore, the content of Ca-Mn-Si-based oxides in the inner side margin 42i located on the inner layer portion 30 side is greater than the content of Ca-Mn-Si-based oxides in the outer side margin 42o located on the second side surface 14 side. The Ca-Mn-Si-based oxides contained in the inner side margin 41i and the inner side margin 42i function as sintering aids during firing. The Ca-Mn-Si-based oxides function as sintering aids, ensuring the sinterability of the inner side margin 41i and the inner side margin 42i. This makes it easy to form dense inner side margin portions 41 i and 42 i. As a result, moisture and the like are less likely to penetrate into the inner side margin portions 41 i and 42 i from the outside, which makes it possible to improve the moisture resistance reliability of the multilayer ceramic capacitor 1.

[0122] Furthermore, since the first outer layer portion 31 and the second outer layer portion 32 are composed of the inner outer layer portion 31i, the inner outer layer portion 32i, the outer outer layer portion 31o, and the outer outer layer portion 32o, which are laminated in the same manner as in the first embodiment, the first outer layer portion 31 and the second outer layer portion 32 in the second embodiment can also achieve the same effects as in the first embodiment.

[0123] Furthermore, in the second embodiment, when the first ceramic green sheet 101 and the second ceramic green sheet 102 are viewed in plan from the lamination (T) direction, the composition of the unsintered dielectric layer 120 in the area overlapping with the area where the inner ceramic pastes 141i and 142i are applied is determined to be MnCO 3 , based on the composition of the unsintered dielectric layer 120 in the area overlapping with the area where the outer ceramic pastes 141o and 142o are applied. ３ The composition of the unfired dielectric layer 120 in the area overlapping with the outer ceramic pastes 141o and 142o is adjusted to have a higher content of Mn compounds such as SiO than the composition of the unfired dielectric layer 120 in the area overlapping with the inner ceramic pastes 141i and 142i. ２ The glass content is adjusted to be high, which further enhances the effect of improving moisture resistance.

[0124] In both the first and second embodiments, a two-terminal multilayer ceramic capacitor 1 having a first external electrode 51 and a second external electrode 52 has been described as an example, but the present invention is not limited to a two-terminal multilayer ceramic capacitor and may be modified in various ways within the scope of its gist.

[0125] Although the embodiments of the present invention have been described above, the present invention is not limited to the embodiments and can be embodied in various forms without departing from the spirit of the present invention. The present invention includes the following combinations.

[0126] <1> A laminate including a plurality of dielectric layers and a plurality of internal electrode layers alternately stacked along a stacking direction, the laminate having first and second main surfaces opposing each other in the stacking direction, first and second side surfaces opposing each other in a width direction perpendicular to the stacking direction, and first and second end surfaces opposing each other in a length direction perpendicular to both the stacking direction and the width direction; a first external electrode provided on the first end surface, the first external electrode being connected to end portions of the plurality of internal electrode layers; and a second external electrode provided on the second end surface, the second external electrode being connected to end portions of the plurality of internal electrode layers, the laminate comprises an inner layer portion in which the plurality of internal electrode layers face each other to form a capacitance, a first outer layer portion located on a first main surface side of the inner layer portion in the lamination direction, a second outer layer portion located on a second main surface side of the inner layer portion in the lamination direction, a first side margin portion located on a first side surface side of the inner layer portion and on a first side surface side of the first outer layer portion in the width direction, and a second side margin portion located on a second side surface side of the inner layer portion and on a second side surface side of the second outer layer portion in the width direction, the first side margin portion and the second side margin portion have an outer side margin portion located on the first side surface side or the second side surface side, and an inner side margin portion located closer to the inner layer portion than the outer side margin portion, and in a cross section of the laminate extending in the lamination direction and the width direction, the calcium silicate content in the outer side margin portion is greater than the calcium silicate content in the inner side margin portion, a multilayer ceramic capacitor in which the content of Ca-Mn-Si-based oxides in the inner side margin portion is greater than the content of Ca-Mn-Si-based oxides in the outer side margin portion; the first outer layer portion and the second outer layer portion have an outer outer layer portion located on the first main surface side or the second main surface side, and an inner outer layer portion located closer to the inner layer portion than the outer outer layer portion; in a cross section of the laminate extending in the stacking direction and the width direction, the content of calcium silicate in the outer outer layer portion is greater than the content of calcium silicate in the inner outer layer portion; and the content of Ca-Mn-Si-based oxides in the inner outer layer portion is greater than the content of Ca-Mn-Si-based oxides in the outer outer layer portion.<2> The multilayer ceramic capacitor according to <1>, wherein, in a cross section of the laminate extending in the stacking direction and the width direction, the amount of misalignment in the width direction between ends of all adjacent internal electrode layers is 5 μm or less. <3> The multilayer ceramic capacitor according to <1> or <2>, wherein the thickness of the outer outer layer portion in the stacking direction is different from the thickness of the inner outer layer portion in the stacking direction, and the thickness of the outer outer layer portion in the stacking direction is greater than the thickness of the inner outer layer portion. <4> The multilayer ceramic capacitor according to any of <1> to <3>, wherein the thickness of the outer outer layer portion in the stacking direction is 10 μm or more and 30 μm or less, and the thickness of the inner outer layer portion in the stacking direction is 5 μm or more and 20 μm or less. <5> The multilayer ceramic capacitor according to any one of <1> to <4>, wherein the width direction thickness of the outer side margin portion is different from the width direction thickness of the inner side margin portion, and the width direction thickness of the outer side margin portion is greater than the width direction thickness of the inner side margin portion. <6> The multilayer ceramic capacitor according to any one of <1> to <5>, wherein the width direction thickness of the outer side margin portion is 3 μm or more and 20 μm or less, and the width direction thickness of the inner side margin portion is 2 μm or more and 20 μm or less. <7> The multilayer ceramic capacitor according to any one of <1> to <6>, wherein the content of calcium silicate in the outer outer layer portion is 5 Atom % or more and 30 Atom % or less higher than the content of calcium silicate in the inner outer layer portion. <8> The multilayer ceramic capacitor according to any one of <1> to <7>, wherein the content of Ca-Mn-Si-based oxide in the inner outer layer portion is 2 Atom % or more and 10 Atom % or less higher than the content of Ca-Mn-Si-based oxide in the outer outer layer portion. <9> The multilayer ceramic capacitor according to any one of <1> to <8>, wherein the content of calcium silicate in the outer side margin portion is 5 Atom % or more and 30 Atom % or less higher than the content of calcium silicate in the inner side margin portion.<10> The multilayer ceramic capacitor according to any one of <1> to <9>, wherein the content of the Ca—Mn—Si-based oxide in the inner side margin portion is 2 Atom % or more and 10 Atom % or less higher than the content of the Ca—Mn—Si-based oxide in the outer side margin portion.

[0127] REFERENCE SIGNS LIST 1 Multilayer ceramic capacitor 10 Laminate 11 First main surface 12 Second main surface 13 First side surface 14 Second side surface 15 First end surface 16 Second end surface 20 Dielectric layer 21 Internal electrode layer 21a First internal electrode layer 21b Second internal electrode layer 30 Internal layer portion 31 First external layer portion 31i Internal external layer portion 31o External external layer portion 32 Second external layer portion 32i Internal external layer portion 32o External external layer portion 41 First side margin portion 41i Internal side margin portion 41o External side margin portion 42 Second side margin portion 42i Internal side margin portion 42o External side margin portion 51 First external electrode 52 Second external electrode

Claims

1. A multilayer ceramic capacitor comprising a plurality of dielectric layers and a plurality of internal electrode layers alternately laminated along a stacking direction, having a first main surface and a second main surface facing each other in the stacking direction, a first side surface and a second side surface facing each other in a width direction orthogonal to the stacking direction, and a first end surface and a second end surface facing each other in a length direction orthogonal to both the stacking direction and the width direction; a first external electrode provided on the first end surface and connected to the ends of the plurality of internal electrode layers; a second external electrode provided on the second end surface and connected to the ends of the plurality of internal electrode layers; wherein the multilayer body includes an inner layer portion in which the plurality of internal electrode layers face each other to form capacitance, a first outer layer portion located on the first main surface side of the inner layer portion in the stacking direction, a second outer layer portion located on the second main surface side of the inner layer portion in the stacking direction, a first side margin portion located on the first side surface side of the inner layer portion and the first side surface side of the first outer layer portion in the width direction, and a second side margin portion located on the second side surface side of the inner layer portion and the second side surface side of the second outer layer portion in the width direction; the first side margin portion and the second side margin portion each have an outer side margin portion located on the first side surface side or the second side surface side, and an inner side margin portion located closer to the inner layer portion than the outer side margin portion; in a cross-section extending in the stacking direction and the width direction of the multilayer body, the content of calcium silicate in the outer side margin portion is more than the content of calcium silicate in the inner side margin portion; the content of the Ca-Mn-Si-based oxide in the inner side margin portion is more than the content of the Ca-Mn-Si-based oxide in the outer side margin portion; the first outer layer portion and the second outer layer portion each have an outer outer layer portion located on the first main surface side or the second main surface side, and an inner outer layer portion located closer to the inner layer portion than the outer outer layer portion; in a cross-section extending in the stacking direction and the width direction of the multilayer body, the content of calcium silicate in the outer outer layer portion is more than the content of calcium silicate in the inner outer layer portion; the content of the Ca-Mn-Si-based oxide in the inner outer layer portion is more than the content of the Ca-Mn-Si-based oxide in the outer outer layer portion.

2. The multilayer ceramic capacitor according to claim 1, wherein in a cross-section extending in the stacking direction and the width direction of the laminate, the displacement amount in the width direction at the width direction end portions of all adjacent inner electrode layers is 5 μm or less.

3. The multilayer ceramic capacitor according to claim 1 or 2, wherein the thickness of the outer outer layer portion in the stacking direction is different from the thickness of the inner outer layer portion in the stacking direction, and the thickness of the outer outer layer portion in the stacking direction is larger than the thickness of the inner outer layer portion.

4. The multilayer ceramic capacitor according to any one of claims 1 to 3, wherein the thickness of the outer outer layer portion in the stacking direction is 10 μm or more and 30 μm or less, and the thickness of the inner outer layer portion in the stacking direction is 5 μm or more and 20 μm or less.

5. The multilayer ceramic capacitor according to any one of claims 1 to 4, wherein the thickness of the outer side margin portion in the width direction is different from the thickness of the inner side margin portion in the width direction, and the thickness of the outer side margin portion in the width direction is larger than the thickness of the inner side margin portion in the width direction.

6. The multilayer ceramic capacitor according to any one of claims 1 to 5, wherein the thickness of the outer side margin portion in the width direction is 3 μm or more and 20 μm or less, and the thickness of the inner side margin portion in the width direction is 2 μm or more and 20 μm or less.

7. The multilayer ceramic capacitor according to any one of claims 1 to 6, wherein the content of calcium silicate in the outer outer layer portion is contained in an amount of 5 Atom% or more and 30 Atom% or less with respect to the content of calcium silicate in the inner outer layer portion.

8. The multilayer ceramic capacitor according to any one of claims 1 to 7, wherein the content of the Ca-Mn-Si based oxide in the inner outer layer portion is contained in an amount of 2 Atom% or more and 10 Atom% or less with respect to the content of the Ca-Mn-Si based oxide in the outer outer layer portion.

9. The multilayer ceramic capacitor according to any one of claims 1 to 8, wherein the content of calcium silicate in the outer side margin portion is contained in an amount of 5 Atom% or more and 30 Atom% or less with respect to the content of calcium silicate in the inner side margin portion.

10. In the inner side margin portion, the content of the Ca—Mn—Si based oxide is contained in an amount of 2 Atom% or more and 10 Atom% or less with respect to the content of the Ca—Mn—Si based oxide in the outer side margin portion. The multilayer ceramic capacitor according to any one of claims 1 to 9.

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