Ceramic Electronic Components

Abstract

A ceramic electronic component in which the outer peripheral layer can be uniformly densified is provided. [Solution] The laminated structure includes a laminated portion in which dielectric layers and internal electrode layers are alternately stacked, and the laminated internal electrode layers are alternately exposed on two opposing end faces; and a cover layer whose main component is ceramic having a perovskite structure. The laminated structure is arranged so that the laminated internal electrode layers cover the ends extending to two side faces other than the two end faces, and the laminated structure includes side margins whose main component is ceramic having a perovskite structure. In at least one region of the cover layer and the side margin, the concentration of at least one specific metal selected from Ag, As, Au, Bi, Co, Cr, Cu, Fe, Ge, In, Ir, Mo, Os, Pd, Pt, Re, Rh, Ru, Se, Sn, Te, W, and Zn gradually decreases from the laminated portion side toward the outside.

Description

[Technical Field]

[0001] The present invention relates to a ceramic electronic component. [Background technology]

[0002] As electronic devices become smaller, further miniaturization is also required for ceramic electronic components such as multilayer ceramic capacitors used in electronic devices. An effective way to increase capacitance, a basic characteristic, is to thin the cover layer and side margin (hereinafter referred to as the outer layer), which do not contribute to capacitance. Meanwhile, the outer layer also serves the function of isolating the capacitance area from the external environment. For example, if moisture in the air comes into direct contact with the capacitance area, the capacitor's insulation will deteriorate, leading to failure. To efficiently prevent moisture penetration from the external environment with a thin outer layer, the outer layer must be dense and free of cracks and pores, eliminating any pathways for moisture. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-258646 Summary of the Invention [Problem to be solved by the invention]

[0004] However, it is difficult to uniformly densify the outer layer. For example, if the main component metal of the internal electrode layer diffuses into the outer layer due to the influence of heat during firing, a difference in the amount of diffusion appears between the region close to the internal electrode layer and the region outside the outer layer, resulting in a distribution in the sintering state within the outer layer.

[0005] The present invention has been made in view of the above-mentioned problems, and has as its object to provide a ceramic electronic component in which the outer peripheral layer can be uniformly densified. [Means for solving the problem]

[0006] A ceramic electronic component according to the present invention comprises a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly made of ceramic having a perovskite structure and internal electrode layers mainly made of Ni are alternately laminated, and the laminated internal electrode layers are formed so as to be alternately exposed at two opposing end faces; and a cover layer provided on at least one of an upper surface and a lower surface in a lamination direction of the laminated structure, the cover layer mainly made of ceramic having a perovskite structure, The cover layer is provided so as to cover the ends extending to the two sides other than the two end faces, and has a side margin whose main component is a ceramic having a perovskite structure, and in at least one region of the cover layer and the side margin, the concentration of at least one specific metal selected from Ag, As, Au, Bi, Co, Cr, Cu, Fe, Ge, In, Ir, Mo, Os, Pd, Pt, Re, Rh, Ru, Se, Sn, Te, W, and Zn gradually decreases from the laminated portion side toward the outside.

[0007] In the ceramic electronic component, when the specific metal is at least one of Au, Bi, Ir, Os, Pd, Pt, Rh, and Ru, the molar concentration of the specific metal in the region may be 0.00001 at% or more and 0.1 at% or less, when the B-site elements of the main component ceramic are taken as 100 at%.

[0008] In the ceramic electronic component, when the specific metal is at least one of Au, Bi, Ir, Os, Pd, Pt, Rh, and Ru, the ratio of the molar concentration of the specific metal to the molar concentration of Ni at the same measurement point in the region may be 0.0001 or more and 1 or less.

[0009] In the ceramic electronic component, when the specific metal is at least one of Cr, Ag, and Cu, the molar concentration of the specific metal in the region may be 0.0001 at% or more and 1 at% or less, when the B-site elements of the main component ceramic are taken as 100 at%.

[0010] In the ceramic electronic component, when the specific metal is at least one of Cr, Ag, and Cu, the ratio of the molar concentration of the specific metal to the molar concentration of Ni at the same measurement point in the region may be 0.0005 or more and 5 or less.

[0011] In the ceramic electronic component, when the specific metal is at least one of Fe, Ge, Sn, and Co, the concentration of the specific metal in the region may be 0.001 at% or more and 20 at% or less, when the B-site elements of the main component ceramic are taken as 100 at%.

[0012] In the ceramic electronic component, when the specific metal is at least one of Fe, Ge, Sn, and Co, the ratio of the molar concentration of the specific metal to the molar concentration of Ni at the same measurement point in the region may be 0.05 or more and 50 or less.

[0013] In the ceramic electronic component, when the specific metal is at least one of In, As, Mo, Re, Se, Te, W, and Zn, the concentration of the specific metal in the region may be 0.01 at% or more and 5 at% or less, when the B-site elements of the main component ceramic are taken as 100 at%.

[0014] In the ceramic electronic component, when the specific metal is at least one of In, As, Mo, Re, Se, Te, W, and Zn, the ratio of the molar concentration of the specific metal to the molar concentration of Ni at the same measurement point in the region may be 0.01 or more and 100 or less.

[0015] In the region of the ceramic electronic component, the ratio of the upper limit / lower limit of the molar concentration of the specific metal may be 1 or more and 100,000 or less.

[0016] In the ceramic electronic component, the region may have a thickness of 10 μm or more and 50 μm or less.

[0017] In the ceramic electronic component, the region may be mainly made of barium titanate. [Effects of the Invention]

[0018] According to the present invention, it is possible to provide a ceramic electronic component in which the outer peripheral layer can be uniformly densified. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 2 is a partial cross-sectional perspective view of a multilayer ceramic capacitor. [Figure 2] FIG. 2 is a cross-sectional view taken along line AA in FIG. [Figure 3] FIG. 2 is a cross-sectional view taken along line BB in FIG. [Figure 4] 10A and 10B are diagrams illustrating a case where pores are formed in a cover layer. [Figure 5] 1(a) to 1(d) are diagrams illustrating the concentration distribution of a specific metal. [Figure 6] (a) to (d) show examples of molar concentration A / molar concentration B of a specific metal in the outer peripheral layer. [Figure 7] 1A to 1C are diagrams illustrating a flow of a method for manufacturing a multilayer ceramic capacitor. [Figure 8] 1(a) and 1(b) are diagrams illustrating the lamination process. [Figure 9] 1A to 1C are diagrams illustrating a lamination process. DETAILED DESCRIPTION OF THE INVENTION

[0020] Hereinafter, embodiments will be described with reference to the drawings.

[0021] (First embodiment) FIG. 1 is a partial cross-sectional perspective view of a multilayer ceramic capacitor 100 in accordance with the first embodiment. FIG. 2 is a cross-sectional view taken along line AA in FIG. 1. FIG. 3 is a cross-sectional view taken along line BB in FIG. 1. As illustrated in FIGS. 1 to 3, the multilayer ceramic capacitor 100 includes a laminated chip 10 having a substantially rectangular parallelepiped shape and external electrodes 20a, 20b provided on two opposing end faces of the laminated chip 10. Of the four faces of the laminated chip 10 other than the two end faces, the two faces other than the top and bottom faces in the stacking direction are referred to as side faces. The external electrodes 20a, 20b extend on the top, bottom and two side faces of the laminated chip 10 in the stacking direction. However, the external electrodes 20a, 20b are spaced apart from each other.

[0022] The multilayer chip 10 includes a laminated structure and a cover layer 13. The laminated structure includes a laminated portion in which dielectric layers 11 and internal electrode layers 12 are alternately stacked. The laminated structure has a generally rectangular parallelepiped shape, and the laminated internal electrode layers 12 are alternately exposed at two end surfaces. As a result, each internal electrode layer 12 is alternately electrically connected to the external electrode 20a and the external electrode 20b. As a result, the multilayer ceramic capacitor 100 has a configuration in which multiple dielectric layers 11 are stacked with the internal electrode layers 12 interposed therebetween. In addition, in the laminated structure of the dielectric layers 11 and the internal electrode layers 12, the internal electrode layer 12 is disposed as the outermost layer in the stacking direction, and the top and bottom surfaces of the laminated structure are covered with a cover layer 13. The cover layer 13 is primarily composed of a ceramic material. For example, the material of the cover layer 13 may be made of the same primarily ceramic material as that of the dielectric layers 11.

[0023] The size of the multilayer ceramic capacitor 100 is, for example, 0.25 mm in length, 0.125 mm in width, and 0.125 mm in height, or 0.4 mm in length, 0.2 mm in width, and 0.2 mm in height, or 0.6 mm in length, 0.3 mm in width, and 0.3 mm in height, or 0.6 mm in length, 0.3 mm in width, and 0.110 mm in height, or 1.0 mm in length, 0.5 mm in width, and 0.5 mm in height, or 1.0 mm in length, 0.5 mm in width, and 0.1 mm in height, or 3.2 mm in length, 1.6 mm in width, and 1.6 mm in height, or 4.5 mm in length, 3.2 mm in width, and 2.5 mm in height, but is not limited to these sizes.

[0024] The dielectric layer 11 has a main phase made of a ceramic material having a perovskite structure represented by the general formula ABO3. 3-α For example, the ceramic material includes BaTiO3 (barium titanate), CaZrO3 (calcium zirconate), CaTiO3 (calcium titanate), SrTiO3 (strontium titanate), MgTiO3 (magnesium titanate), BaTiO3 (barium titanate) which forms a perovskite structure, 1-x-y Ca x Sr y Ti 1-z Zr z At least one of the following can be selected and used: O3 (0≦x≦1, 0≦y≦1, 0≦z≦1). 1-x-y Ca x Sr y Ti 1-z Zr z O3 includes barium strontium titanate, barium calcium titanate, barium zirconate, barium titanate zirconate, calcium titanate zirconate and barium calcium titanate zirconate.

[0025] In this embodiment, for example, the thickness of each dielectric layer 11 is 0.05 μm to 5 μm, or 0.1 μm to 3 μm, or 0.2 μm to 1 μm. The thickness of the dielectric layers 11 can be measured by observing the cross section of the multilayer ceramic capacitor 100 with a scanning electron microscope (SEM), measuring the thickness at 10 points for each of 10 different dielectric layers 11, and deriving the average value of all the measurement points.

[0026] The internal electrode layers 12 are mainly composed of Ni. The thickness of the internal electrode layers 12 is, for example, 10 nm or more and 1000 nm or less, 20 nm or more and 500 nm or less, or 50 nm or more and 300 nm or less. The thickness of the internal electrode layers 12 can be measured by observing the cross section of the multilayer ceramic capacitor 100 with an SEM, measuring the thickness at 10 points for each of 10 different internal electrode layers 12, and deriving the average value of all the measurement points.

[0027] 2, the region where the internal electrode layer 12 connected to the external electrode 20a and the internal electrode layer 12 connected to the external electrode 20b face each other is a region where capacitance is generated in the multilayer ceramic capacitor 100. Therefore, this region where capacitance is generated is referred to as a capacitance region 14. In other words, the capacitance region 14 is a region where adjacent internal electrode layers 12 connected to different external electrodes face each other.

[0028] The region where the internal electrode layers 12 connected to the external electrode 20a face each other without an internal electrode layer 12 connected to the external electrode 20b interposed therebetween is called the end margin 15. The region where the internal electrode layers 12 connected to the external electrode 20b face each other without an internal electrode layer 12 connected to the external electrode 20a interposed therebetween is also the end margin 15. In other words, the end margin 15 is the region where the internal electrode layers 12 connected to the same external electrode face each other without an internal electrode layer 12 connected to a different external electrode interposed therebetween. The end margin 15 is a region where no capacitance is generated.

[0029] As illustrated in Figure 3, in the laminated chip 10, the regions extending from the two side surfaces of the laminated chip 10 to the internal electrode layers 12 are referred to as side margins 16. In other words, the side margins 16 are regions provided to cover the ends of the multiple internal electrode layers 12 stacked in the above-mentioned laminated structure that extend to the two side surfaces. The side margins 16 are also regions that do not generate electrical capacitance. The laminated structure included in the above-mentioned laminated chip 10 corresponds to the capacitive region 14 and the side margins 16.

[0030] Since the cover layer 13 and the side margin 16 cover the outer periphery of the capacitance region 14 , the cover layer 13 and the side margin 16 will be hereinafter collectively referred to as an outer periphery layer 60 .

[0031] If moisture in the air comes into direct contact with the capacitance region 14, the insulation of the multilayer ceramic capacitor 100 may deteriorate, leading to failure. By providing the peripheral layer 60, the capacitance region 14 is isolated from the external environment, thereby providing insulation. On the other hand, in order to make the multilayer ceramic capacitor 100 smaller and larger capacity, it is effective to thin the peripheral layer 60, which does not contribute to capacitance. Therefore, in order to efficiently prevent the penetration of moisture from the external environment with a thin peripheral layer 60, it is necessary to make the peripheral layer 60 dense and free of cracks and pores, thereby eliminating paths for moisture.

[0032] Each part in the laminated chip 10 is obtained by sintering powder materials through firing. In the capacitance region 14, sintering of the dielectric layer 11 is accelerated due to the influence of the Ni powder used to fire the internal electrode layers 12. In contrast, the peripheral layer 60 does not have a portion corresponding to the internal electrode layers 12, so sintering is slower than in the capacitance region 14. This may result in an increase in pores in the peripheral layer 60. Furthermore, if Ni, the main metal component of the internal electrode layers 12, diffuses into the peripheral layer 60 due to the influence of heat during firing, a difference in the amount of Ni diffusion appears between the region close to the internal electrode layers 12 and the region outside the peripheral layer 60, which may result in a distribution in the sintering state within the peripheral layer 60.

[0033] FIG. 4 is a diagram illustrating an example in which pores 17 are formed in the cover layer 13. Hatching of the cover layer 13 has been omitted in FIG. 4. In the example of FIG. 4, multiple pores 17 are dispersed in the cover layer 13. If pores 17 are formed in the cover layer 13 in this manner, sufficient insulation may not be obtained. Furthermore, there are fewer pores near the capacitance region 14 and more pores on the outer side, which may result in a distribution in the sintering state within the outer circumferential layer 60. Note that while increasing the firing temperature can sufficiently promote sintering of the outer circumferential layer 60, increasing the firing temperature may result in over-sintering of the internal electrode layer 12, reducing the continuity rate of the internal electrode layer 12 and degrading the capacitance characteristics.

[0034] Therefore, in this embodiment, at least one region of the peripheral layer 60 has a configuration that can uniformly densify the internal electrode layers 12 while suppressing a decrease in the continuity ratio. Specifically, at least one region of the peripheral layer 60 contains a specific metal in addition to a main component ceramic having a perovskite structure. The specific metal is at least one of Ag, As, Au, Bi, Co, Cr, Cu, Fe, Ge, In, Ir, Mo, Os, Pd, Pt, Re, Rh, Ru, Se, Sn, Te, W, and Zn. The inclusion of these specific metals in the peripheral layer 60 accelerates sintering of the peripheral layer 60 during firing. This suppresses the formation of pores 17 in the peripheral layer 60. The accelerated sintering of the peripheral layer 60 due to the inclusion of the specific metal in the peripheral layer 60 is believed to be due to at least one of the following reasons: the specific metal accelerates sintering more rapidly than Ni; or the specific metal is more likely to exert its sintering effect over a longer distance than Ni.

[0035] Furthermore, in at least one region of the peripheral layer 60, a concentration gradient is formed in which the concentration of the specific metal gradually decreases from the capacitance region 14 side to the peripheral (surface) side. With this configuration, sintering progresses from the side closer to the capacitance region 14 toward the outside, so components from the inside (organic components such as binders) can be efficiently removed before the outside is densified and closed. This suppresses the formation of pores 17 in the peripheral layer 60, allowing the peripheral layer 60 to be uniformly densified. As a result, the moisture resistance reliability of the multilayer ceramic capacitor 100 is improved.

[0036] 5(a) to 5(d) are diagrams illustrating the concentration distribution of a specific metal when Ni is used as the main component metal for the internal electrode layers 12, barium titanate is used as the main component ceramic for the dielectric layers 11 and the peripheral layer 60, and a concentration gradient of the specific metal is formed in the peripheral layer 60. The concentration of the specific metal at each measurement point can be measured using LA-ICP (laser ablation inductively coupled plasma mass spectrometry). The measurement points are spaced apart at intervals of, for example, 1000 nm. The thickness of the peripheral layer 60 is, for example, 60 μm. To reduce noise, the data may be smoothed by averaging multiple adjacent points (for example, nine points).

[0037] 5(a) to 5(d), the horizontal axis represents the distance from the internal electrode layer 12 in the outer peripheral layer 60 (distance from the capacitance region 14), and the vertical axis represents the molar concentration A (at%) of a specific metal in logarithm when the B-site element (Ti in barium titanate) of the main component ceramic of the outer peripheral layer 60 is taken as 100 at%. The distance from the internal electrode layer 12 represents the separation distance from the capacitance region 14 in the stacking direction for the cover layer 13, and represents the separation distance from the capacitance region 14 in the width direction of the internal electrode layer 12 for the side margin 16.

[0038] In Figure 5(a), Au is used as the specific metal. In Figure 5(b), Cr is used as the specific metal. In Figure 5(c), Fe is used as the specific metal. In Figure 5(d), In is used as the specific metal.

[0039] As illustrated in Figures 5(a) to 5(d), the molar concentration A of the specific metal has a monotonically decreasing gradient, gradually decreasing (decreasing) with increasing distance from the volume region 14. By forming such a concentration gradient for the specific metal, it is possible to uniformly densify the outer circumferential layer 60. Note that the term "gradually decreasing" as used herein includes a continuous decrease, as well as an overall decrease with repeated ups and downs when the concentration is measured at multiple sample points from the volume region 14 toward the outside.

[0040] 5(a) to 5(d), the Ni concentration distribution is also plotted. As illustrated in FIGS. 5(a) to 5(d), the Ni molar concentration B has a monotonically decreasing slope, gradually decreasing (decreasing) with increasing distance from the capacitance region 14. Ni is contained in the outer peripheral layer 60 because Ni diffuses from the internal electrode layers 12 during the firing process. Here, "gradually decreasing" includes not only a continuous decrease, but also an overall decrease with repeated ups and downs when the concentration is measured at multiple sample points from the capacitance region 14 to the outside.

[0041] 6(a) to 6(d) illustrate the molar concentration A / molar concentration B (hereinafter, A / B ratio) of a specific metal in the outer peripheral layer 60. The horizontal axis represents the distance from the internal electrode layer 12 (distance from the capacitance region 14) within the outer peripheral layer 60, and the vertical axis represents the A / B ratio in logarithm. The A / B ratio is the ratio of molar concentration A to molar concentration B at the same measurement point. As illustrated in FIG. 6(a), when Au is used as the specific metal, the A / B ratio exhibits a monotonically increasing slope, gradually increasing (gradually increasing) with increasing distance from the capacitance region 14. As illustrated in FIG. 6(b), when Cr is used as the specific metal, the A / B ratio exhibits a monotonically increasing slope, gradually increasing (gradually increasing) with increasing distance from the capacitance region 14. As illustrated in FIG. 6(c), when Fe is used as the specific metal, the A / B ratio tends to remain within a predetermined range, regardless of the distance from the capacitance region 14. As shown in FIG. 6(d), when In is used as the specific metal, the A / B ratio has a monotonically increasing slope, gradually increasing (gradually increasing) with increasing distance from the capacitance region 14.

[0042] The results of FIGS. 5(a) to 5(d) and 6(a) to 6(d) are shown in Table 1. Table 1 includes the lower limit (at%), upper limit (at%), and concentration gradient shape of the molar concentration A of the specific metal in the outer peripheral layer 60; the lower limit (at%), upper limit (at%), and concentration gradient shape of the molar concentration B of Ni in the outer peripheral layer 60; and the lower limit, upper limit, and gradient shape of the A / B ratio in the outer peripheral layer 60. Bi, Ir, Os, Pd, Pt, Rh, and Ru are thought to behave similarly to Au because they have a similar balance point between the ease of sintering relative to the outer peripheral layer 60 and the ease of diffusion into the outer peripheral layer 60. Ag and Cu are thought to behave similarly to Cr because they have a similar balance point between the ease of sintering relative to the outer peripheral layer 60 and the ease of diffusion into the outer peripheral layer 60. Ge, Sn, and Co are thought to behave similarly to Fe because they have a similar balance point between the ease of sintering relative to the outer peripheral layer 60 and the ease of diffusion into the outer peripheral layer 60. As, Mo, Re, Se, Te, W, and Zn are thought to behave similarly to In because they have a similar balance between ease of sintering to the outer peripheral layer 60 and ease of diffusion into the outer peripheral layer 60. [Table 1]

[0043] If the molar concentration A of the specific metal in the outer peripheral layer 60 is too low, the sintering of the outer peripheral layer 60 may not be accelerated sufficiently. Therefore, it is preferable to set a lower limit for the molar concentration A of the specific metal in the outer peripheral layer 60. For example, when the specific metal is at least one of Au, Bi, Ir, Os, Pd, Pt, Rh, and Ru, the molar concentration A of the specific metal in the outer peripheral layer 60 is preferably 0.00001 at% or more, more preferably 0.00005 at% or more, and even more preferably 0.0001 at% or more. For example, when the specific metal is at least one of Cr, Ag, and Cu, the molar concentration A of the specific metal in the outer peripheral layer 60 is preferably 0.0001 at% or more, more preferably 0.0005 at% or more, and even more preferably 0.001 at% or more. For example, when the specific metal is at least one of Fe, Ge, Sn, and Co, the molar concentration A of the specific metal in the outer layer 60 is preferably 0.001 at% or more, more preferably 0.005 at% or more, and even more preferably 0.01 at% or more. For example, when the specific metal is at least one of In, As, Mo, Re, Se, Te, W, and Zn, the molar concentration A of the specific metal in the outer layer 60 is preferably 0.01 at% or more, more preferably 0.05 at% or more, and even more preferably 0.1 at% or more.

[0044] If the molar concentration of the specific metal in the outer layer 60 is too high, it may degrade the insulating properties. Therefore, it is preferable to set an upper limit on the molar concentration of the specific metal in the outer layer 60. For example, when the specific metal is at least one of Au, Bi, Ir, Os, Pd, Pt, Rh, and Ru, the molar concentration A of the specific metal in the outer layer 60 is preferably 0.1 at% or less, more preferably 0.05 at% or less, and even more preferably 0.01 at% or less. For example, when the specific metal is at least one of Cr, Ag, and Cu, the molar concentration A of the specific metal in the outer layer 60 is preferably 1 at% or less, more preferably 0.5 at% or less, and even more preferably 0.1 at% or less. For example, when the specific metal is at least one of Fe, Ge, Sn, and Co, the molar concentration A of the specific metal in the outer layer 60 is preferably 20 at% or less, more preferably 10 at% or less, and even more preferably 2 at% or less. For example, when the specific metal is at least one of In, As, Mo, Re, Se, Te, W, and Zn, the molar concentration A of the specific metal in the outer layer 60 is preferably 5 at% or less, more preferably 1 at% or less, and even more preferably 0.5 at% or less.

[0045] In order to form a sufficient gradient in the molar concentration A of the specific metal in the outer peripheral layer 60, it is preferable to set a lower limit on the ratio of the upper limit / lower limit of the molar concentration A in the outer peripheral layer 60. For example, the ratio of the upper limit / lower limit of the molar concentration A in the outer peripheral layer 60 is preferably 1 or more, more preferably 1.2 or more, and even more preferably 1.5 or more. On the other hand, if the gradient set in the molar concentration A of the specific metal in the outer peripheral layer 60 is too large, there is a risk that the sintering of the outermost periphery will not be completed in time. Therefore, it is preferable to set an upper limit on the ratio of the upper limit / lower limit of the molar concentration A in the outer peripheral layer 60. For example, the ratio of the upper limit / lower limit of the molar concentration A in the outer peripheral layer 60 is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less. In the outer peripheral layer 60, the molar concentration A gradually decreases from the volume region 14 side toward the outside, so the upper / lower limit ratio of the molar concentration A corresponds to the ratio of the molar concentration A closest to the volume region 14 side to the molar concentration A at the outermost side in the outer peripheral layer 60.

[0046] If the A / B ratio in the outer peripheral layer 60 is too low, sintering may not proceed sufficiently. Therefore, it is preferable to set a lower limit for the A / B ratio in the outer peripheral layer 60. For example, when the specific metal is at least one of Au, Bi, Ir, Os, Pd, Pt, Rh, and Ru, the A / B ratio in the outer peripheral layer 60 is preferably 0.001 or greater, more preferably 0.0005 or greater, and even more preferably 0.001 or greater. For example, when the specific metal is at least one of Cr, Ag, and Cu, the A / B ratio in the outer peripheral layer 60 is preferably 0.0005 or greater, more preferably 0.001 or greater, and even more preferably 0.005 or greater. For example, when the specific metal is at least one of Fe, Ge, Sn, and Co, the A / B ratio in the outer peripheral layer 60 is preferably 0.05 or greater, more preferably 0.1 or greater, and even more preferably 0.5 or greater. For example, when the specific metal is at least one of In, As, Mo, Re, Se, Te, W, and Zn, the A / B ratio in the outer layer 60 is preferably 0.01 or greater, more preferably 0.05 or greater, and even more preferably 0.1 or greater.

[0047] If the A / B ratio in the outer peripheral layer 60 is too high, insulation properties may be degraded. Therefore, it is preferable to set an upper limit to the A / B ratio in the outer peripheral layer 60. For example, when the specific metal is at least one of Au, Bi, Ir, Os, Pd, Pt, Rh, and Ru, the A / B ratio in the outer peripheral layer 60 is preferably 1 or less, more preferably 0.5 or less, and even more preferably 0.1 or less. For example, when the specific metal is at least one of Cr, Ag, and Cu, the A / B ratio in the outer peripheral layer 60 is preferably 5 or less, more preferably 1 or less, and even more preferably 0.5 or less. For example, when the specific metal is at least one of Fe, Ge, Sn, and Co, the A / B ratio in the outer peripheral layer 60 is preferably 50 or less, more preferably 10 or less, and even more preferably 5 or less. For example, when the specific metal is at least one of In, As, Mo, Re, Se, Te, W, and Zn, the A / B ratio in the outer layer 60 is preferably 100 or less, more preferably 50 or less, and even more preferably 10 or less.

[0048] If the peripheral layer 60 is too thin, it may not be possible to sufficiently prevent moisture from entering from the external environment. Therefore, it is preferable to set a lower limit on the thickness of the peripheral layer 60. For example, the thickness of the peripheral layer 60 is preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more. On the other hand, if the peripheral layer 60 is too thick, the area that does not generate capacitance will become large. Therefore, it is preferable to set an upper limit on the thickness of the peripheral layer 60. For example, the thickness of the peripheral layer 60 is preferably 50 μm or less, preferably 45 μm or less, and even more preferably 40 μm or less. Note that the thickness of the peripheral layer 60 refers to the thickness in the stacking direction for the cover layer 13, and the thickness in the width direction of the internal electrode layer 12 for the side margin 16. In addition, the thickness of the cover layer 13 and the side margin 16 can be measured by observing the cross section of the multilayer ceramic capacitor 100 with an SEM (scanning electron microscope), measuring the thickness at 10 different points for each of the cover layer 13 and the side margin 16, and deriving the average value.

[0049] In addition, when there are multiple types of metals, the molar concentration A of a specific metal refers to the total molar concentration of those multiple metals.

[0050] Next, a description will be given of a method for manufacturing the multilayer ceramic capacitor 100. FIG.

[0051] (raw powder production process) First, raw material powders for forming the dielectric layer 11, cover layer 13, and side margin 16 are prepared. The A-site and B-site elements contained in the dielectric layer 11, cover layer 13, and side margin 16 are typically present in the form of a sintered compact of ABO3 particles. For example, BaTiO3 is a tetragonal compound with a perovskite structure and exhibits a high dielectric constant. BaTiO3 is generally obtained by synthesizing barium titanate by reacting a titanium source such as titanium dioxide with a barium source such as barium carbonate. Various methods are known for synthesizing the ceramics that form the main components of the dielectric layer 11, cover layer 13, and side margin 16, including the solid-state method, the sol-gel method, and the hydrothermal method. Any of these methods can be used in this embodiment.

[0052] The resulting ceramic powder is then doped with a predetermined additive compound depending on the purpose, such as oxides of Mg, manganese (Mn), vanadium (V), Cr, rare earth elements (Y, samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), and ytterbium (Yb)), oxides containing Co, Ni, lithium (Li), boron (B), sodium (Na), potassium (K), or silicon (Si), or glasses containing cobalt, nickel, lithium, boron, sodium, potassium, or silicon.

[0053] For example, a ceramic material is prepared by wet-mixing a ceramic raw material powder with a compound containing an additive compound, followed by drying and pulverization. For example, the ceramic material obtained as described above may be pulverized as necessary to adjust the particle size, or may be combined with a classification process to adjust the particle size. A raw material powder is obtained by the above steps.

[0054] (Lamination process) Next, a binder such as polyvinyl butyral (PVB) resin, an organic solvent such as ethanol or toluene, and a plasticizer are added to the raw material powder produced in the raw material powder production step and wet mixed. Using the obtained slurry, a dielectric green sheet 52 is coated on a substrate 51 by, for example, a die coater method or a doctor blade method, and then dried. The substrate 51 is, for example, a PET (polyethylene terephthalate) film.

[0055] Next, as illustrated in Fig. 8(a), internal electrode patterns 53 are formed on the dielectric green sheet 52. In Fig. 8(a), as an example, four layers of internal electrode patterns 53 are formed at predetermined intervals on the dielectric green sheet 52. The dielectric green sheet 52 on which the internal electrode patterns 53 are formed is defined as a lamination unit.

[0056] Next, while peeling off the dielectric green sheet 52 from the substrate 51, the lamination units are laminated as shown in FIG. 8(b).

[0057] Next, a predetermined number of cover sheets 54 are laminated on the top and bottom of the laminate obtained by laminating the lamination units, thermocompression-bonded, and cut to a predetermined chip size (e.g., 1.0 mm x 0.5 mm). In the example of FIG. 8(b), cutting is performed along the dotted lines. The cover sheet 54 can be obtained, similarly to the dielectric green sheet 52, by wet-mixing the raw material powder produced in the raw material powder production step with a binder such as polyvinyl butyral (PVB) resin, an organic solvent such as ethanol or toluene, and a plasticizer, and then coating the resulting slurry on the substrate 51 by a die coater method or a doctor blade method and drying it.

[0058] Each cover sheet 54 is doped with at least one specific metal selected from the group consisting of Ag, As, Au, Bi, Co, Cr, Cu, Fe, Ge, In, Ir, Mo, Os, Pd, Pt, Re, Rh, Ru, Se, Sn, Te, W, and Zn. The amount of specific metal added to each cover sheet 54 is varied. The cover sheet 54 closest to the stack of the stack unit has the highest concentration of the specific metal, and the concentration gradually decreases with increasing distance from the stack of the stack unit. This allows a gradient in the concentration of the specific metal to be formed.

[0059] The region corresponding to the side margin 16 may be attached or coated on the side surface of the laminate of the above-mentioned lamination unit. Specifically, as illustrated in FIG. 9, a laminate is obtained by alternately stacking dielectric green sheets 52 and internal electrode patterns 53 having the same width as the dielectric green sheets 52. Next, a plurality of side margin sheets 55 may be attached to the side surface of the laminate. Similar to the dielectric green sheets 52, the side margin sheets 55 can be obtained by wet-mixing the raw material powder prepared in the raw material powder preparation step with a binder such as polyvinyl butyral (PVB) resin, an organic solvent such as ethanol or toluene, and a plasticizer, and then coating the resulting slurry on the substrate 51 by a die coater method or a doctor blade method and drying it.

[0060] A specific metal is added to each side margin sheet 55. The amount of specific metal added to each side margin sheet 55 is made different. The concentration of the specific metal is made highest in the side margin sheet 55 closest to the stack of the stack unit, and the concentration of the specific metal gradually decreases as the sheet moves away from the stack of the stack unit. In this way, a gradient can be formed in the concentration of the specific metal.

[0061] (Firing process) The ceramic laminate thus obtained was subjected to binder removal treatment in an N2 atmosphere, after which a metal paste that would become the base layer of the external electrodes 20a, 20b was applied by dipping, and the ceramic laminate was heated in an atmosphere with an oxygen partial pressure of 10 -5 ~10 -8The mixture is then fired in a reducing atmosphere at 1100 to 1300° C. for 10 minutes to 2 hours at 1 atm. In this way, the multilayer ceramic capacitor 100 is obtained.

[0062] (Reoxidation treatment process) Thereafter, a re-oxidation treatment may be performed at 600°C to 1000°C in an N2 gas atmosphere.

[0063] (Plating process) Thereafter, the external electrodes 20a, 20b may be coated with a metal such as Cu, Ni, or Sn by plating.

[0064] According to the manufacturing method of the multilayer ceramic capacitor 100 of this embodiment, by varying the concentration of the specific metal in each cover sheet 54, it is possible to form a concentration gradient in the cover layer 13 such that the concentration of the specific metal gradually decreases from the capacitance region 14 side toward the outer periphery (surface) side. Also, by varying the concentration of the specific metal in each side margin sheet 55, it is possible to form a concentration gradient in the side margin 16 such that the concentration of the specific metal gradually decreases from the capacitance region 14 side toward the outer periphery (surface) side.

[0065] In the above embodiments, a multilayer ceramic capacitor has been described as an example of a ceramic electronic component, but the present invention is not limited to this. For example, other electronic components such as a varistor or a thermistor may also be used. [Example]

[0066] The multilayer ceramic capacitor according to the embodiment was fabricated and its characteristics were examined.

[0067] (Comparative Example 1) A dielectric green sheet containing barium titanate as the primary ceramic component was prepared, and Ni paste was printed on its surface as an internal electrode pattern. 13 layers of the dielectric green sheet with the internal electrode pattern formed were stacked on top of a previously prepared cover sheet. No specific metal was added to the cover sheet. The resulting product was then compressed, cut, coated with metal paste for the external electrodes, and fired to obtain a multilayer ceramic capacitor element.

[0068] Example 1 Ten cover sheets each 1 / 10 the specified thickness were prepared, and different amounts of Fe were added to each sheet to achieve the desired gradient composition. These 10 sheets were stacked in order. The cover sheets were stacked so that the cover sheet closest to the internal electrode had the greatest amount of Fe added, and the Fe content gradually decreased. The 10 stacked cover sheets were combined into one cover sheet. Thirteen dielectric green sheets with internal electrode patterns printed on the surface of the cover sheets were stacked. The other processes were the same as in Comparative Example 1.

[0069] Example 2 Ten cover sheets each 1 / 10 the specified thickness were prepared, and different amounts of Au were added to each sheet to achieve the desired gradient composition. These 10 sheets were stacked in order. The cover sheets were stacked so that the cover sheet closest to the internal electrode had the greatest amount of Au added, and the amount of Au gradually decreased. The 10 stacked cover sheets were combined into one cover sheet. Thirteen dielectric green sheets with internal electrode patterns printed on the surface of the cover sheets were stacked. The other processes were the same as in Comparative Example 1.

[0070] Example 3 Ten cover sheets each 1 / 10 the specified thickness were prepared, and different amounts of Cr were added to each sheet to achieve the desired gradient composition. These 10 sheets were stacked in order. The cover sheets were stacked so that the cover sheet closest to the internal electrode had the greatest amount of Cr added, with the amount gradually decreasing. The 10 stacked cover sheets were combined into one cover sheet. Thirteen layers of dielectric green sheets with internal electrode patterns printed on the surface of the cover sheets were stacked. The other processes were the same as in Comparative Example 1.

[0071] Example 4 Ten cover sheets each 1 / 10 the specified thickness were prepared, and different amounts of In were added to each sheet to achieve the desired gradient composition. These 10 sheets were stacked in order. The cover sheets were stacked so that the cover sheet closest to the internal electrode had the greatest amount of In added, and the amount of In gradually decreased. The 10 stacked cover sheets were combined into one cover sheet. Thirteen dielectric green sheets with internal electrode patterns printed on the surface of the cover sheets were stacked. The other processes were the same as in Comparative Example 1.

[0072] (Comparative Example 2) Ten cover sheets each 1 / 10 the specified thickness were prepared, and the same amount of Fe was added to each sheet to avoid a gradient composition. These 10 sheets were stacked in order to form a single cover sheet. Thirteen layers of dielectric green sheets with internal electrode patterns printed on the surfaces of the cover sheets were stacked. The amount of Fe added to each cover sheet was greater than in Example 1. The other processes were the same as in Comparative Example 1.

[0073] (Comparative Example 3) Ten cover sheets each 1 / 10 the specified thickness were prepared, and the same amount of Cr was added to each sheet to avoid a gradient composition. These 10 sheets were stacked in order to form a single cover sheet. 13 layers of dielectric green sheets with internal electrode patterns printed on the surface of the cover sheets were stacked. The amount of Cr added to each cover sheet was greater than in Example 3. The other processes were the same as in Comparative Example 1.

[0074] For each of Examples 1 to 4 and Comparative Examples 2 and 3, the molar concentration A of the specific metal and the molar concentration B of Ni in the cover layer were measured using LA-ICP. The measurement points were spaced 1000 nm apart. For Comparative Example 1, no specific metal was added to the cover sheet, so neither the molar concentration A nor the molar concentration B was measured. For each of Examples 1 to 4 and Comparative Examples 2 and 3, the concentration of the specific metal in the cover layer gradually decreased with increasing distance from the capacity region.

[0075] In Example 1, the minimum value of the molar concentration A of the specific metal was 0.01 at%, the maximum value of the molar concentration A was 2 at%, the minimum value of the A / B ratio was 0.8, and the maximum value of the A / B ratio was 3. In Example 2, the minimum value of the molar concentration A of the specific metal was 0.0001 at%, the maximum value of the molar concentration A was 0.004 at%, the minimum value of the A / B ratio was 0.001, and the maximum value of the A / B ratio was 0.1. In Example 3, the minimum value of the molar concentration A of the specific metal was 0.002 at%, the maximum value of the molar concentration A was 0.03 at%, the minimum value of the A / B ratio was 0.005, and the maximum value of the A / B ratio was 0.2. In Example 4, the minimum value of the molar concentration A of the specific metal was 0.2 at%, the maximum value of the molar concentration A was 0.3 at%, the minimum value of the A / B ratio was 0.1, and the maximum value of the A / B ratio was 10. In Comparative Example 2, the molar concentration A of the specific metal was 0.3 at% throughout the entire peripheral layer, the minimum A / B ratio was 0.06, and the maximum A / B ratio was 300. In Comparative Example 3, the molar concentration A of the specific metal was 0.2 at% throughout the entire peripheral layer, the minimum A / B ratio was 0.04, and the maximum A / B ratio was 200. The results are shown in Table 2. [Table 2]

[0076] The moisture resistance reliability was examined for each of Examples 1 to 4 and Comparative Examples 1 to 3. Specifically, a moisture resistance load test was conducted. If the 500-hour test time was cleared, the moisture resistance reliability was judged to be good (◯). If failure occurred before the 500-hour test time, the moisture resistance reliability was judged to be poor (×). In all of Examples 1 to 4, the moisture resistance reliability was judged to be good (◯). This is thought to be because a configuration was obtained in which the concentration of the specific metal gradually decreased from the capacitance region side toward the outside in the peripheral layer. In Comparative Example 1, the moisture resistance reliability was judged to be poor (×). This is thought to be because the specific metal was not added to the peripheral layer.

[0077] The capacitance characteristics were examined for each of Examples 1 to 4 and Comparative Examples 1 to 3. Specifically, capacitance measurements were performed using an LCR meter. If the designed capacity was met, the capacitance characteristics were judged to be good "◯". If the designed capacity was not met, the capacitance characteristics were judged to be poor "×". In all of Examples 1 to 4, the capacitance characteristics were judged to be good "◯". This is thought to be because in Examples 1 to 4, a configuration was obtained in which the molar concentration A was in an appropriate range.

[0078] Although the embodiments of the present invention have been described in detail above, the present invention is not limited to such specific embodiments, and various modifications and variations are possible within the scope of the gist of the present invention as defined in the claims. [Explanation of symbols]

[0079] 10 stacked chips 11 Dielectric layer 12 Internal electrode layer 13 Cover Layer 14 capacity area 15 End Margin 16 Side Margin 17 Pore 20a,20b external electrode 51 Base material 52 Dielectric green sheet 53 Internal electrode pattern 60 outer layer 100 Multilayer ceramic capacitors

Claims

1. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the concentration of at least one specific metal selected from Ag, As, Au, Bi, Co, Cr, Cu, Fe, Ge, In, Ir, Mo, Os, Pd, Pt, Re, Rh, Ru, Se, Sn, Te, W, and Zn gradually decreases from the laminated portion side toward the outside, When the specific metal is at least one of Au, Bi, Ir, Os, Pd, Pt, Rh, and Ru, the molar concentration of the specific metal in the region is 0.00005 at% or more and 0.05 at% or less when the B-site elements of the main component ceramic are taken as 100 at%.

2. 2. The ceramic electronic component according to claim 1, wherein the specific metal is Au, and the molar concentration of the specific metal in the region is 0.0001 or more and 0.004 or less.

3. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the concentration of at least one specific metal selected from Ag, As, Au, Bi, Co, Cr, Cu, Fe, Ge, In, Ir, Mo, Os, Pd, Pt, Re, Rh, Ru, Se, Sn, Te, W, and Zn gradually decreases from the laminated portion side toward the outside, A ceramic electronic component characterized in that, when the specific metal is at least one of Au, Bi, Ir, Os, Pd, Pt, Rh, and Ru, the ratio of the molar concentration of the specific metal to the molar concentration of Ni at the same measurement point in the region is 0.005 or more and 0.5 or less.

4. 4. The ceramic electronic component according to claim 3, wherein the specific metal is Au, and the ratio of the molar concentration of the specific metal to the molar concentration of Ni at the same measurement point in the region is 0.001 or more and 0.1 or less.

5. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the concentration of at least one specific metal selected from Ag, As, Au, Bi, Co, Cr, Cu, Fe, Ge, In, Ir, Mo, Os, Pd, Pt, Re, Rh, Ru, Se, Sn, Te, W, and Zn gradually decreases from the laminated portion side toward the outside, When the specific metal is at least one of Cr, Ag, and Cu, the molar concentration of the specific metal in the region is 0.0005 at% or more and 0.5 at% or less, when the B-site elements of the main component ceramic are taken as 100 at%.

6. 6. The ceramic electronic component according to claim 5, wherein the specific metal is Cr, and the molar concentration of the specific metal in the region is 0.002 or more and 0.03 or less.

7. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the concentration of at least one specific metal selected from Ag, As, Au, Bi, Co, Cr, Cu, Fe, Ge, In, Ir, Mo, Os, Pd, Pt, Re, Rh, Ru, Se, Sn, Te, W, and Zn gradually decreases from the laminated portion side toward the outside, When the specific metal is at least one of Cr, Ag, and Cu, the ratio of the molar concentration of the specific metal to the molar concentration of Ni at the same measurement point in the region is 0.001 or more and 1 or less.

8. 8. The ceramic electronic component according to claim 7, wherein the specific metal is Cr, and the ratio of the molar concentration of the specific metal to the molar concentration of Ni at the same measurement point in the region is 0.005 or more and 0.2 or less.

9. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the concentration of at least one specific metal selected from Ag, As, Au, Bi, Co, Cr, Cu, Fe, Ge, In, Ir, Mo, Os, Pd, Pt, Re, Rh, Ru, Se, Sn, Te, W, and Zn gradually decreases from the laminated portion side toward the outside, When the specific metal is at least one of Fe, Ge, Sn, and Co, the concentration of the specific metal in the region is 0.005 at% or more and 10 at% or less, when the B-site elements of the main component ceramic are taken as 100 at%.

10. 10. The ceramic electronic component according to claim 9, wherein the specific metal is Fe, and the molar concentration of the specific metal in the region is 0.01 or more and 2 or less.

11. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the concentration of at least one specific metal selected from Ag, As, Au, Bi, Co, Cr, Cu, Fe, Ge, In, Ir, Mo, Os, Pd, Pt, Re, Rh, Ru, Se, Sn, Te, W, and Zn gradually decreases from the laminated portion side toward the outside, When the specific metal is at least one of Fe, Ge, Sn, and Co, the ratio of the molar concentration of the specific metal to the molar concentration of Ni at the same measurement point in the region is 0.1 or more and 10 or less.

12. 12. The ceramic electronic component according to claim 11, wherein the specific metal is Fe, and in the region, the ratio of the molar concentration of the specific metal to the molar concentration of Ni at the same measurement point is 0.8 or more and 3 or less.

13. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the concentration of at least one specific metal selected from Ag, As, Au, Bi, Co, Cr, Cu, Fe, Ge, In, Ir, Mo, Os, Pd, Pt, Re, Rh, Ru, Se, Sn, Te, W, and Zn gradually decreases from the laminated portion side toward the outside, When the specific metal is at least one of In, As, Mo, Re, Se, Te, W, and Zn, the concentration of the specific metal in the region is 0.05 at% or more and 1 at% or less, when the B-site elements of the main component ceramic are taken as 100 at%.

14. 14. The ceramic electronic component according to claim 13, wherein the specific metal is In, and the molar concentration of the specific metal in the region is 0.2 or more and 0.3 or less.

15. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the concentration of at least one specific metal selected from Ag, As, Au, Bi, Co, Cr, Cu, Fe, Ge, In, Ir, Mo, Os, Pd, Pt, Re, Rh, Ru, Se, Sn, Te, W, and Zn gradually decreases from the laminated portion side toward the outside, When the specific metal is at least one of In, As, Mo, Re, Se, Te, W, and Zn, the ratio of the molar concentration of the specific metal to the molar concentration of Ni at the same measurement point in the region is 0.05 or more and 50 or less.

16. 16. The ceramic electronic component according to claim 15, wherein the specific metal is In, and the ratio of the molar concentration of the specific metal to the molar concentration of Ni at the same measurement point in the region is 0.1 or more and 10 or less.

17. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the concentration of Au gradually decreases from the stacked portion side toward the outside, A ceramic electronic component characterized in that in the region, the concentration of Au is 0.01 at % or less in a range of 0 μm or more and 20 μm or less from the end of the laminated portion side to the outside.

18. 18. The ceramic electronic component according to claim 17, wherein in the region, the concentration of Au is 0.0001 at % or more in a range of 0 μm or more and 20 μm or less from the end of the laminated portion side to the outside.

19. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the Cr concentration gradually decreases from the stacked portion side toward the outside, A ceramic electronic component characterized in that in the region, the Cr concentration is 0.05 at % or less in a range of 0 μm or more and 20 μm or less from the end of the laminated portion side to the outside.

20. 20. The ceramic electronic component according to claim 19, wherein the Cr concentration in the region is 0.002 at % or more in a range of 0 μm or more and 20 μm or less from the end of the laminated portion side to the outside.

21. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the Fe concentration gradually decreases from the stacked portion side toward the outside, A ceramic electronic component characterized in that in the region, the concentration of Fe is 5 at % or less in a range of 0 μm or more and 20 μm or less from the end of the laminated portion side to the outside.

22. 22. The ceramic electronic component according to claim 21, wherein the Fe concentration in the region is 0.1 at % or more in a range of 0 μm or more and 20 μm or less from the end of the laminated portion side to the outside.

23. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the concentration of In gradually decreases from the stacked portion side toward the outside, A ceramic electronic component characterized in that in the region, the concentration of In is 0.5 at % or less in a range of 0 μm or more and 20 μm or less from the end of the laminated portion side to the outside.

24. 24. The ceramic electronic component according to claim 23, wherein in the region, the In concentration is 0.1 at % or more in a range of 0 μm or more and 20 μm or less from the end on the laminated portion side to the outside.

25. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the concentration of Au gradually decreases from the stacked portion side toward the outside, a ratio of the molar concentration of Au to the molar concentration of Ni at the same measurement point in a range of 0 μm or more and 20 μm or less from the end of the laminated portion side to the outside in the region is 0.01 or less.

26. 26. The ceramic electronic component according to claim 25, wherein in the region, in a range of 0 μm or more and 20 μm or less from the end on the stacked portion side to the outside, the ratio of the molar concentration of Au to the molar concentration of Ni at the same measurement point is 0.001 or more.

27. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the Cr concentration gradually decreases from the stacked portion side toward the outside, a ratio of the molar concentration of Cr to the molar concentration of Ni at the same measurement point in a range of 0 μm or more and 20 μm or less from the end of the laminated portion side to the outside in the region is 0.1 or less.

28. 28. The ceramic electronic component according to claim 27, wherein in the region, in a range of 0 μm or more and 20 μm or less from the end on the stacked portion side to the outside, the ratio of the molar concentration of Cr to the molar concentration of Ni at the same measurement point is 0.002 or more.

29. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the Fe concentration gradually decreases from the stacked portion side toward the outside, a ratio of the molar concentration of Au to the molar concentration of Ni at the same measurement point in a range of 0 μm or more and 20 μm or less from the end of the laminated portion side to the outside in the region is 5 or less.

30. 30. The ceramic electronic component according to claim 29, wherein in the region, in a range of 0 μm or more and 20 μm or less from the end on the stacked portion side to the outside, a ratio of the molar concentration of Fe to the molar concentration of Ni at the same measurement point is 1 or more.

31. a laminated structure having a substantially rectangular parallelepiped shape, including a laminated portion in which dielectric layers mainly composed of ceramic having a perovskite structure and internal electrode layers mainly composed of Ni are alternately laminated, and in which the laminated plurality of internal electrode layers are alternately exposed on two opposing end surfaces; a cover layer provided on at least one of an upper surface and a lower surface in a stacking direction of the laminated structure, the cover layer containing a ceramic having a perovskite structure as a main component; the laminated structure is provided so that the laminated plurality of internal electrode layers cover end portions extending to two side surfaces other than the two end surfaces, and includes side margins whose main component is a ceramic having a perovskite structure; In at least one region of the cover layer and the side margin, the concentration of In gradually decreases from the stacked portion side toward the outside, a ratio of the molar concentration of In to the molar concentration of Ni at the same measurement point in the region within a range of 0 μm or more and 20 μm or less from the end of the laminated portion side to the outside, the ratio being 1 or less.

32. 32. The ceramic electronic component according to claim 31, wherein in the region, in a range of 0 μm or more and 20 μm or less from the end on the stacked portion side to the outside, the ratio of the molar concentration of In to the molar concentration of Ni at the same measurement point is 0.05 or more.

33. 33. The ceramic electronic component according to claim 1, wherein the region has a thickness of 10 μm or more and 50 μm or less.

34. 34. The ceramic electronic component according to claim 1, wherein the ceramic material mainly comprising the region is barium titanate.

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