Multilayer ceramic capacitor

Abstract

The present disclosure relates to a multilayer ceramic capacitor comprising a laminate having: an inner layer part in which internal ceramic layers and internal electrode layers are alternately laminated; external ceramic layers that are disposed on both sides of the inner layer part in the lamination direction; and lateral surface ceramic parts that are disposed on both sides of the inner layer part and the external ceramic layers in the width direction orthogonal to the lamination direction. The thickness of each of the lateral surface ceramic parts is 20 μm or less. In a cross section parallel to the width direction and the lamination direction of the laminate, when a region surrounded by a first extension line extending in the lamination direction along lateral surfaces of the inner layer part, a second extension line extending in the width direction along an external-ceramic-layer side surface of the outermost internal electrode layer in the inner layer part, and a contour line on the surface side of the lateral surface ceramic parts is defined as a corner portion, and the corner portion is divided into the surface side and the inner layer part side, the porosity on the surface side of the corner portion is 0.50% or less, and the porosity on the inner layer part side of the corner portion is higher than the porosity on the surface side of the corner portion.

Description

Multilayer ceramic capacitor

[0001] This disclosure relates to multilayer ceramic capacitors.

[0002] Japanese Patent Publication No. 2014-204116 (Patent Document 1) discloses a multilayer ceramic capacitor in which a first side margin portion and a second side margin portion with an average thickness of 18 μm or less are divided into two regions by a virtual line connecting the center point of the distance between the end of the internal electrode and the point where the extension line of the internal electrode touches the first side surface or the second side surface, and the region adjacent to the internal electrode is called S1, and the porosity of S1 is called P1, such that 1 ≤ P1 ≤ 20.

[0003] Japanese Patent Publication No. 2014-204116

[0004] The multilayer ceramic capacitors disclosed in Patent Document 1 are produced in large quantities, and during transportation, the capacitors may come into contact with each other, potentially causing cracks or chips. In particular, when the thickness of the side margin is reduced to about 20 μm or less, the occurrence of cracks and chips at the corners is significant.

[0005] The object of this disclosure is to provide a multilayer ceramic capacitor in which cracking and chipping are suppressed at the corners.

[0006] A multilayer ceramic capacitor according to an embodiment of the present disclosure comprises a laminate having an inner layer portion in which an inner ceramic layer and an inner electrode layer are alternately laminated, an outer ceramic layer arranged on both sides in the lamination direction of the inner layer portion, and a side ceramic portion arranged on both sides in the width direction perpendicular to the lamination direction of the inner layer portion and the outer ceramic layer. The thickness of the side ceramic portion is 20 μm or less. In a cross section of the laminate parallel to the width direction and the lamination direction, a corner is defined as the region enclosed by a first extension line extending in the lamination direction along the side of the inner layer portion, a second extension line extending in the width direction along the outermost inner electrode layer on the outer ceramic layer side of the inner layer portion, and the contour line on the surface side of the side ceramic portion. When the corner is divided into a surface side and an inner layer side, the pore ratio on the surface side of the corner is 0.50% or less, and the pore ratio on the inner layer side of the corner is higher than the pore ratio on the surface side of the corner.

[0007] According to this disclosure, it is possible to provide a multilayer ceramic capacitor in which cracking and chipping are suppressed.

[0008] Figure 1 is a perspective view showing the external appearance of a multilayer ceramic capacitor. Figure 2 is a cross-sectional view of the multilayer ceramic capacitor shown in Figure 1, taken from the direction of the arrow II-II. Figure 3 is a cross-sectional view of the multilayer ceramic capacitor shown in Figure 1, taken from the direction of the arrow III-III. Figure 4 is a cross-sectional view of the multilayer ceramic capacitor to illustrate the corners. Figure 5 is a cross-sectional view to illustrate the crack surface. Figure 6 is a schematic diagram of the crack surface viewed from the direction of the arrow in Figure 5. Figure 7 is a schematic cross-sectional view to illustrate the amount of indentation in the side ceramic portion. Figure 8 is a diagram illustrating the location where the pore ratio of the multilayer ceramic capacitor in the embodiment was measured.

[0009] The multilayer ceramic capacitor of this disclosure will be described with reference to Figures 1 to 3. Figure 1 is a perspective view showing the external appearance of the multilayer ceramic capacitor. Figure 2 is a cross-sectional view of the multilayer ceramic capacitor of Figure 1 taken from the direction of the arrow II-II. Figure 3 is a cross-sectional view of the multilayer ceramic capacitor of Figure 1 taken from the direction of the arrow III-III.

[0010] The multilayer ceramic capacitor 100 shown in Figures 1 to 3 comprises a laminate 110 and an external electrode 120. The laminate 110 has an inner layer portion 150 including an inner ceramic layer 130 and an inner electrode layer 140 that are alternately stacked one layer at a time along the stacking direction T, and an outer ceramic layer 160 arranged on both sides of the inner layer portion 150 in the stacking direction T. The outer ceramic layer 160 includes a first outer ceramic layer 160A and a second outer ceramic layer 160B.

[0011] The laminate 110 has side ceramic portions 170 arranged on both sides in the width direction W perpendicular to the lamination direction T. The side ceramic portions 170 include a first side ceramic portion 170A and a second side ceramic portion 170B.

[0012] The laminate 110 has a first main surface 161 and a second main surface 162 that are opposite each other in the stacking direction T, a first side surface 171 and a second side surface 172 that are opposite each other in the width direction W which is perpendicular to the stacking direction T, and a first end surface 181 and a second end surface 182 that are opposite each other in the length direction L which is perpendicular to both the stacking direction T and the width direction W. The laminate 110 can be divided into an inner layer 150, an outer ceramic layer 160, and a side ceramic portion 170. The inner ceramic layer 130, the outer ceramic layer 160, and the side ceramic portion 170 are collectively referred to as the ceramic portion.

[0013] The internal electrode layer 140 includes a first internal electrode layer 140A connected to a first external electrode 120A, and a second internal electrode layer 140B connected to a second external electrode 120B. A capacitor is formed when the first internal electrode layer 140A and the second internal electrode layer 140B face each other via the internal ceramic layer 130. The multilayer ceramic capacitor 100 can be described as a plurality of capacitors connected in parallel via the first external electrode 120A and the second external electrode 120B. As shown in Figure 3, the positions of the end faces at both ends of the internal electrode layer 140 in the width direction W may be the same or substantially the same. In the cross-section shown in Figure 3, the side ceramic portion 170, the inner layer portion 150, and the outer ceramic layer 160 can be distinguished based on the positions of the end faces at both ends of the internal electrode layer 140 in the width direction W. The number of stacked internal ceramic layers 130 may be, for example, 200 to 1000. The number of layers of the internal electrode layer 140 may be, for example, 200 to 1000.

[0014] The ceramic portion is manufactured using ceramic material. The inner ceramic layer 130, the outer ceramic layer 160, and the side ceramic portion 170 each contain the same or different perovskite-type compounds as their main components. The perovskite-type compound has the formula: ABO ３ The compound may be a perovskite-type compound represented by the formula [wherein A contains barium (Ba), B contains at least one of titanium (Ti) and zirconium (Zr), and O is an oxygen atom].

[0015] Examples of perovskite-type compounds include barium titanate (BaTiO2).３ Perovskite-type compounds of the [system name] and barium zirconate (BaZrO ３ ), and perovskite-type compounds of the [system name] etc. can be mentioned. BaTiO ３ The perovskite-type compound of the BaTiO ３ system, for example, BaTiO ３ and Ba of BaTiO ２＋ and at least one of Ti ４＋ is replaced by other ions such as Ca ２＋ and Zr ４＋ etc. are perovskite-type compounds etc. The perovskite-type compound of the BaZrO ３ system, for example, BaZrO ３ and Ba of BaZrO ３ and at least one of Zr ２＋ is replaced by other ions such as Ca ４＋ and Zr ２＋ etc. are perovskite-type compounds etc.

[0016] The content of the perovskite-type compound in the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic part 170 may be, for example, 90% by mass or more, or 95% by mass or more, or 99% by mass or more, based on the total mass of the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic part 170.

[0017] When the perovskite-type compound contained in the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic part 170 is a perovskite-type compound represented by ABO ３ , the molar ratio A / B of the A-site component and the B-site component of the perovskite-type compound represented by ABO ３ contained in the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic part 170 is preferably 1.004 or more and 1.010 or less. By setting A / B within the above range, grain growth during firing can be suppressed and the generation of coarse particles can be suppressed.

[0018] ​​The multilayer ceramic capacitor 100 has a side ceramic portion 170 with a thickness of 20 μm or less. The thickness of the side ceramic portion 170 may be 18 μm or less. The thickness of the side ceramic portion 170 is the maximum thickness in the width direction W.

[0019] The thickness of the outer ceramic layer 160 may be, for example, 40 μm or less, or 35 μm or less, or 32 μm or less. The thickness of the outer ceramic layer 160 is the maximum thickness in the lamination direction T.

[0020] The internal ceramic layer 130 may have a thickness of, for example, 0.3 μm or more and 0.6 μm or less. When the ceramic part has a thickness within the above range, the particle size and density tend to become uniform during the firing process, and the difference in density within the ceramic part tends to become smaller.

[0021] The ceramic portion may have pores (gaps or holes). In the multilayer ceramic capacitor 100, in a cross section parallel to the width direction W and the stacking direction T of the laminate 110 (hereinafter also referred to as the WT cross section), the region enclosed by a first extension line extending in the stacking direction T along the side surface 151 of the inner layer portion 150, a second extension line extending in the width direction along the surface of the outermost inner electrode layer 140 of the inner layer portion 150 on the outer ceramic layer 160 side, and the contour line on the surface side of the side ceramic portion 170 is defined as a corner, and when the corner is divided into a surface side and an inner layer portion side, the pore ratio on the surface side of the corner is 0.50% or less. By appropriately controlling the pore ratio at the corner, the multilayer ceramic capacitor of this disclosure makes it possible to suppress cracking and chipping at the corner even though the thickness of the side ceramic portion is 20 μm or less. Therefore, in order to suppress crack formation while maintaining moisture resistance, and to suppress crack propagation, it is preferable that the pore ratio on the inner layer side of the corner is higher than that on the surface side of the corner.

[0022] The pore ratio is the ratio of the pore area to the area per field of view when observing a corner using a scanning electron microscope (SEM). The pore ratio can be determined, for example, by performing SEM observation such that the area per field of view is a 13 μm × 9 μm area of ​​the corner.

[0023] The corner will be explained with reference to Figure 4. Figure 4 is a schematic cross-sectional view showing an enlarged view of the region including the corner in the WT cross-section. External electrodes are not shown in Figure 4. In Figure 4, the corner R is the region enclosed by a first extension line E1 extended in the stacking direction T along the side surface 151 of the inner layer 150, a second extension line E2 extended in the width direction W along the surface 152 of the outermost inner electrode layer 140S on the outer ceramic layer 160 side of the inner layer 150, and a contour line E3 on the surface side of the side ceramic portion 170. The corner R can be divided into a surface side and an inner layer side with the curve E4 as the boundary, when the curve E4 is defined as the midpoint of the straight line connecting the intersection point O of the first extension line E1 and the second extension line E2 to a point on the contour line E3. In measuring the pore ratio, when the region for measuring the pore ratio on the surface side of the corner R (the region per field of view in SEM observation) is defined as region Rs, and the region for measuring the pore ratio on the inner layer side of the corner R (the region per field of view in SEM observation) is defined as region Ri, region Rs may be in contact with the surface contour line E3, and region Ri may be in contact with the intersection point O. Furthermore, for example, in measuring the pore ratio of a relatively small corner R, regions Ri and Rs may overlap or be in contact with each other, and at least one of region Rs and region Ri may extend beyond at least one of curve E4 and contour line E3. In measuring the pore ratio, if at least one of region Rs and region Ri extends beyond at least one of curve E4 and contour line E3, the pore ratio can be measured in regions Rs and Ri other than the region that extends beyond curve E4 and contour line E3. Regions Rs and Ri can each be, for example, regions on the line E5 that passes through intersection point O and a point on contour line E3, with an angle of 45° with the second extension line E2.

[0024] The pore ratio on the surface side of the corner radius is preferably 0.46% or less, more preferably 0.30% or less, and even more preferably 0.25% or less, from the viewpoint of suppressing cracking and chipping. The pore ratio on the surface side of the corner may be, for example, 0.10% or more.

[0025] The pore ratio of the corner R can be controlled by adjusting, for example, the firing treatment conditions (such as firing temperature, firing time, heating rate, etc.) and the annealing treatment conditions (such as annealing temperature, annealing time, heating rate, etc.). Further, the pore ratio of the corner R can be controlled by adjusting the number of sheets of the green sheet for the side surface ceramic part and their respective compositions, which will be described later.

[0026] The pore ratio on the inner layer side of the corner R is higher than that on the surface side of the corner R. Since the pore ratio on the inner layer side of the corner R is higher than that on the surface side of the corner R, the progress of cracks is likely to be suppressed. Cracks due to fractures may lead to a short circuit when they reach the effective layer. According to the present disclosure, not only the presence or absence of simple fractures and chips at the corners but also the progress of cracks can be suppressed.

[0027] The suppression of crack progress will be described while referring to FIGS. 5 and 6. FIG. 5 is a schematic cross-sectional view for explaining a crack surface when a crack occurs at a corner in a WT cross-section. FIG. 6 is a schematic view when looking at the crack surface from the direction of the arrow in FIG. 5. As shown in FIG. 6, when a crack passes through a pore, the pore divides the surface into two during the formation of the crack surface, but a step occurs when they are integrated again. At this time, by forming the step, the energy required for the crack to extend is dispersed. The outer ceramic layer and the side surface ceramic part are designed to have fewer pores overall to ensure moisture resistance. Among them, if the pores on the outer (surface) side are made fewer, the probability of crack occurrence tends to decrease. On the other hand, when a certain number of pores exist on the inner (inner layer) side, the extension of cracks is suppressed and the direction of cracks is likely to be dispersed.

[0028] The ratio of the pore ratio on the inner layer side of the corner R to the pore ratio on the surface side of the corner R is preferably 1.10 to 1.80, more preferably 1.10 to 1.50, from the viewpoint of suppressing the progress of cracks.

[0029] In the WT cross-section, when the area of ​​the outer ceramic layer 160 and the side ceramic portion 170 other than the corner radius (hereinafter also referred to as the planar region) is divided into a surface side and an inner layer side, the pore ratio on the surface side of the planar region may be, for example, 3.0% or less. A pore ratio of 3.0% or less on the surface side of the planar region tends to improve moisture resistance. From the viewpoint of moisture resistance, the pore ratio on the surface side of the planar region is preferably 1.0% or less. The surface side and the inner layer side of the planar region can be divided equally by dividing the thickness of the outer ceramic layer 160 and the side ceramic portion 170 in half. Preferably, the pore ratio on the surface side of the planar region is measured in the area including the center of the section sandwiched between the two corners in the WT cross-section. The area where the pore ratio on the surface side of the planar region is measured may be in contact with the surface. The area where the pore ratio on the inner layer side of the planar region is measured may be in contact with the inner layer.

[0030] The pore ratio on the inner layer side of the flat region may be higher than that on the surface side of the flat region. When the pore ratio on the inner layer side of the flat region is higher than that on the surface side of the flat region, crack propagation tends to be more easily suppressed.

[0031] When manufacturing the side ceramic portion 170, two or more layers of the side ceramic portion green sheet described later may be attached. In this case, two or more different curved surfaces may be created at the boundary of each layer at the corner, and a recess may occur at the corner. Figure 7 schematically shows a recessed corner in a WT cross-section when two side ceramic portion green sheets are attached. As shown in Figure 7, when the depth of the recess Lc is defined as the length of the perpendicular line drawn from the point of deepest recess to the straight line E6 tangent to the contour lines of the two different curved surfaces at the corner, the depth of the recess Lc can be, for example, 1 μm or less. When the depth of the recess Lc is within the above range, cracking and chipping at the corner tend to be suppressed.

[0032] The internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 can further contain a rare earth element (Re). When the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 further contain a rare earth element, the perovskite-type compound may be a perovskite-type compound in which some of the elements in the crystal lattice are ions of the rare earth element Re. ３＋ It may be a perovskite-type compound substituted by.

[0033] The rare earth element can contain at least one selected from the group consisting of scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu). The inner layer portion 150, the external ceramic layer 160, and the side ceramic portion 170 preferably contain at least one selected from the group consisting of Dy, Y, Gd, Tb, Ho, and Er, and more preferably contain Dy.

[0034] The content of the rare earth element in the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 may be 0.5 mol part or more and 3.0 mol parts or less, preferably 1.0 mol part or more and 2.0 mol parts or less, and more preferably 1.5 mol parts or more and 1.7 mol parts or less, respectively, with respect to 100 mol parts of the perovskite-type compound contained in the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170.

[0035] When the internal ceramic layer 130 contains Dy, the content of Dy may be 1.5 mol parts or more and 1.7 mol parts or less with respect to 100 mol parts of the perovskite-type compound contained in the internal ceramic layer 130.

[0036] If the outer ceramic layer 160 and the side ceramic portion 170 contain Dy, the Dy content may be 1.5 moles or more and 1.7 moles or less per 100 moles of the perovskite-type compound contained in the outer ceramic layer 160 and the side ceramic portion 170, respectively.

[0037] The internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 may further contain at least one other element selected from the group consisting of silicon (Si), aluminum (Al), manganese (Mn), nickel (Ni), iron (Fe), copper (Cu), vanadium (V), and magnesium (Mg). By including these other elements, the density of the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 can be controlled during the firing process.

[0038] The internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 preferably further contain Mn from the viewpoint of density. When the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 further contain Mn, the Mn content in the external ceramic layer 160 and the side ceramic portion 170 can be greater than the Mn content in the internal ceramic layer 130. This tends to reduce the difference in density between the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170.

[0039] The internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 preferably further contain Si from the viewpoint of density. When the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 further contain Si, the Si content in the external ceramic layer 160 and the side ceramic portion 170 can be greater than the Si content in the internal ceramic layer 130. This tends to reduce the difference in density between the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170.

[0040] The internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 preferably further contain Al from the viewpoint of density. When the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 further contain Al, the Al content in the external ceramic layer 160 and the side ceramic portion 170 can be greater than the Al content in the internal ceramic layer 130. This tends to reduce the difference in density between the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170.

[0041] The internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 more preferably contain Mn, Si, and Al from the viewpoint of density. When the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 further contain Mn, Si, and Al, the content of Mn, Si, and Al in the external ceramic layer 160 and the side ceramic portion 170 can be higher than the content of Mn, Si, and Al in the internal ceramic layer 130, respectively. This tends to reduce the difference in density between the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170.

[0042] If the internal ceramic layer 130 further contains Mn, Si, and Al, the Mn content may be, for example, 0.1 moles to 0.2 moles per 100 moles of the perovskite-type compound, the Si content may be, for example, 1.0 mole to 1.4 moles, and the Al content may be, for example, 0.06 moles to 0.1 moles.

[0043] If the outer ceramic layer 160 and the side ceramic portion 170 further contain Mn, Si, and Al, the Mn content may be, for example, 0.3 moles or more and 0.9 moles or less, the Si content may be, for example, 1.1 moles or more and 2.5 moles or less, and the Al content may be, for example, 0.12 moles or more and 0.25 moles or less, per 100 moles of the perovskite-type compound.

[0044] In the outer ceramic layer 160 and the side ceramic portion 170, the ratio of the Mn content to the total content of Mn, Si, and Al [Mn / (Mn+Si+Al)] can be, for example, 0.09 or more and 0.42 or less.

[0045] The internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 preferably further contain Ni. If the internal ceramic layer 130 further contains Ni, the Ni content may be, for example, 1.3 moles to 1.7 moles per 100 moles of the perovskite-type compound. If the external ceramic layer 160 and the side ceramic portion 170 further contain Ni, the Ni content may be, for example, 0.4 moles or less per 100 moles of the perovskite-type compound.

[0046] The outer ceramic layer 160 and the side ceramic portion 170 preferably further contain V. When the outer ceramic layer 160 and the side ceramic portion 170 further contain V, the V content may be, for example, 0.03 moles or more and 0.07 moles or less per 100 moles of the perovskite-type compound.

[0047] The content of rare earth elements and other elements in the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 can be determined from the mixing ratio of the starting materials. Furthermore, the content of rare earth elements and other elements in the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 can be quantified by methods such as X-ray fluorescence analysis (XRF), inductively coupled plasma emission spectroscopy (ICP-AES), and energy-dispersive X-ray spectroscopy (EDX). When quantifying by EDX, for example, observation images at a magnification of 150,000x using a scanning transmission electron microscope (STEM / EDX) can be used.

[0048] The internal electrode layer 140 mainly contains Ni. The main component is the component that has the largest mass content among the constituent components. The internal electrode layer 140 may be an alloy containing Ni. The internal electrode layer 140 may further contain tin (Sn).

[0049] The thickness of the internal electrode layer 140 in the lamination direction T may be, for example, 0.2 μm or more and 0.5 μm or less. When the thickness of the internal electrode layer 140 in the lamination direction T is within the above range, the common material tends to reach the edges in the width direction more easily during the firing process.

[0050] The laminate 110 may further have end face ceramic portions 180 arranged on both sides in the length direction L, which is perpendicular to both the lamination direction T and the width direction W. The end face ceramic portion 180 has a first end face ceramic portion 180A and a second end face ceramic portion 180B. The thickness of the end face ceramic portion 180 may be, for example, 15 μm or more and 50 μm or less. The composition of the end face ceramic portion 180 is the same as the composition description for the outer ceramic layer 160 and the side ceramic portion 170.

[0051] In this specification, the thicknesses of the internal ceramic layer 130, the internal electrode layer 140, the external ceramic layer 160, the side ceramic portion 170, and the end ceramic portion 180 are measured in an SEM image of the cross-section of the laminate 110 in the lamination direction T.

[0052] The ceramic portion may contain multiple grains. The inner ceramic layer 130, the outer ceramic layer 160, and the side ceramic portion 170 may contain multiple grains. A grain is a particle surrounded by a grain boundary and is also called a crystal grain.

[0053] The particle sizes of multiple grains can be measured using a SEM. In this specification, the particle size of a single grain refers to the diameter of a circle having an area equal to the area of ​​the grain's cross-section in an SEM observation image of a cross-section parallel to the stacking direction T and width direction W of the inner layer 150 (hereinafter also referred to as the area circle equivalent diameter). In this specification, in the particle size distribution of the area circle equivalent diameters of multiple grains measured from an SEM observation image of a cross-section parallel to the stacking direction T and width direction W of the inner layer 150, the particle size that accumulates to 50% by area is defined as D50, and the particle size that accumulates to 99% by area is defined as D99. The SEM observation image of the above cross-section of the inner layer 150 may be, for example, an SEM observation image at 40,000x magnification. The cumulative particle size distribution of multiple grains is determined from the particle sizes of 200 or more grains. Note that it is not necessary for one SEM observation image to contain 200 or more grains; it is sufficient if the total number of grains contained in multiple SEM observation images is 200 or more.

[0054] The inner layer 150 is a cross-section of the laminate 110, and in a cross-section parallel to the lamination direction T and the width direction W, it has a central region 150B, a region near the outer ceramic layer 150A, and a region near the side ceramic portion 150C. The central region 150B, the region near the outer ceramic layer 150A, and the region near the side ceramic portion 150C will be described with reference to Figure 3. The central region 150B is a region located near the center in the lamination direction T and the width direction W in a cross-section parallel to the lamination direction T and the width direction W. The central region 150B may be, for example, a region within a 3.0 μm × 3.0 μm square centered on the intersection of a center line that bisects the inner layer 150 in the lamination direction T and a center line that bisects the inner layer 150 in the width direction W. The region 150A near the outer ceramic layer is the region located in the center of the width direction W of the inner ceramic layer 130 closest to the outer ceramic layer 160 and the inner ceramic layer 130 second closest to the outer ceramic layer 160. The center of the width direction W may be, for example, a region of 1.5 μm on both sides (total width 3.0 μm) from the center line that divides the inner layer 150 in the width direction W. The region 150C near the side ceramic part is the region 3.0 μm inward from the width direction end of the inner electrode layer 140 (i.e., the boundary between the inner layer 150 and the side ceramic part 170), and is located in the center of the stacking direction T. The center of the stacking direction T may be, for example, a region of 1.5 μm on both sides (total thickness 3.0 μm) from the center line that divides the inner layer 150 in the stacking direction T. In Figure 3, only the region 150A near the outer ceramic layer on the first main surface 161 side is shown, but a region 150A near the outer ceramic layer also exists on the second main surface 162 side. The grain size of the grains contained in the region 150A near the outer ceramic layer may be measured from either of the two regions 150A near the outer ceramic layer. Also, in Figure 3, only the region 150C near the side ceramic portion on the second side surface 172 side is shown, but a region 150C near the side ceramic portion also exists on the first side surface 171 side. The grain size of the grains contained in the region 150C near the side ceramic portion may be measured from either of the two regions 150C near the side ceramic portion.

[0055] In the inner layer 150, the sintering behavior during the firing process differs between the central region 150B, the region near the outer ceramic layer 150A, and the region near the side ceramic portion 150C. As a result, the grain size of the grains contained in each region may differ. Specifically, the grain size of the grains contained in the region near the outer ceramic layer 150A or the region near the side ceramic portion 150C tends to be larger than that of the grains contained in the central region 150B.

[0056] The grain D50 in the central region 150B, the region near the outer ceramic layer 150A, and the region near the side ceramic portion 150C is 80 nm to 140 nm, preferably 90 nm to 135 nm, and more preferably 100 nm to 130 nm.

[0057] The D99 / D50 of the grains included in the central region 150B, the region near the outer ceramic layer 150A, and the region near the side ceramic portion 150C is 1.4 or more and 2.2 or less, preferably 2.1 or less, and more preferably 2.0 or less.

[0058] The D50 of the grains contained in the outer ceramic layer 160 is between 180 nm and 360 nm, preferably between 200 nm and 340 nm, and more preferably between 220 nm and 320 nm.

[0059] The D50 of the grains contained in the side ceramic portion 170 is 180 nm to 360 nm, preferably 200 nm to 340 nm, and more preferably 220 nm to 320 nm.

[0060] The grain size is determined by the starting material (e.g., BaTiO) used to fabricate the internal ceramic layer 130. ３ The above range can be achieved by selecting the particle size and composition of the powder, adjusting the content of rare earth elements and other elements, and adjusting the firing temperature and heating rate in the firing process of the multilayer ceramic capacitor manufacturing method described later.

[0061] The external electrodes 120 are provided on the surface of the laminate 110. The external electrodes 120 are arranged on both sides in the longitudinal direction L perpendicular to the stacking direction T of the laminate 110 and are connected to the internal electrode layer 140. In the multilayer ceramic capacitor 100, the external electrodes 120 include a first external electrode 120A and a second external electrode 120B.

[0062] The first external electrode 120A is formed on the first end face 181 of the laminate 110 so as to be electrically connected to the first internal electrode layer 140A. The first external electrode 120A extends from the first end face 181 to the first main surface 161 and the second main surface 162, and to the first side surface 171 and the second side surface 172. The second external electrode 120B is formed on the second end face 182 of the laminate 110 so as to be electrically connected to the second internal electrode layer 140B. The second external electrode 120B extends from the second end face 182 to the first main surface 161 and the second main surface 162, and to the first side surface 171 and the second side surface 172.

[0063] The first external electrode 120A and the second external electrode 120B each have, for example, a base electrode layer and a plating layer disposed on the base electrode layer. The base electrode layer includes, for example, at least one selected from a sintered body layer, a conductive resin layer, and a metal thin film layer.

[0064] The sintered body layer is formed by baking a paste containing glass powder and metal powder, and includes a glass portion and a metal portion. The glass constituting the glass portion is B ２ O ３ -SiO ２ - Examples include BaO-based glass. The metal constituting the metal part may be at least one selected from Ni, Cu, and Ag, or an alloy containing such metal. Multiple sintered layers may be formed with different components. Furthermore, the sintered layers may be fired simultaneously with the laminate in the manufacturing method described later, or they may be baked on after the laminate has been fired.

[0065] The conductive resin layer comprises conductive particles, such as metal nanoparticles, and a resin portion. The metal constituting the metal nanoparticles may be at least one selected from Ni, Cu, and Ag, or an alloy containing these metals. The resin constituting the resin portion may be an epoxy-based thermosetting resin. The conductive resin layer may be formed in multiple layers of different components.

[0066] The metal thin film layer is a layer with a thickness of 1 μm or less, formed by a thin film formation method such as sputtering or vapor deposition, in which metal nanoparticles are deposited. Examples of metals constituting the metal thin film layer include at least one selected from Ni, Cu, Ag, and Au, or alloys containing these metals. Multiple metal thin film layers may be formed with different components.

[0067] Examples of metals constituting the plating layer include at least one selected from Ni, Cu, Ag, Au, and tin (Sn), or alloys containing such metals. The plating layer may be formed in multiple layers with different components.

[0068] The first external electrode 120A and the second external electrode 120B may each be a plating layer directly provided on the laminate 110 and directly connected to the corresponding internal electrode layer 140 described above.

[0069] The multilayer ceramic capacitor 100 is manufactured, for example, as follows. First, slurries for the internal ceramic layer, the external ceramic layer, and the side ceramic portion are prepared to produce the green sheets for the internal ceramic layer, the external ceramic layer, and the side ceramic portion, respectively. Each element can be mixed in an oxide or carbonate state to achieve the composition of the internal ceramic layer 130, the external ceramic layer 160, and the side ceramic portion 170 as described above.

[0070] The outer ceramic layer and the side ceramic portion can be formulated to have higher amounts of Mn, Si, and Al compared to the inner ceramic layer, from the viewpoint of density. In the outer ceramic layer 160 and the side ceramic portion 170, the content of Si, Mn, and Al can be increased in that order (Si > Mn > Al). The composition values ​​of each slurry can be adjusted according to the chip size of the multilayer ceramic capacitor 100. The composition of each slurry can be adjusted to exclude Mg, or to include Mg.

[0071] The slurry is formed into a sheet on a carrier film using a die coater, gravure coater, or microgravure coater, thereby forming a green sheet for the internal ceramic layer, a green sheet for the external ceramic layer, and a green sheet for the side ceramic portion.

[0072] Next, a conductive paste mainly composed of Ni is screen printed onto a green sheet for the internal ceramic layer to form a conductive paste film (conductor pattern) that will serve as the internal electrode. The green sheets for the internal ceramic layer, on which the conductive paste film is formed, are stacked so that the ends of the conductive paste film are drawn in alternating directions to create a laminate for the inner layer. A co-material can be included in the conductive paste. The co-material may or may not contain Mg.

[0073] Next, green sheets for the outer ceramic layer are stacked above and below the laminate for the inner layer, sandwiching it in between. After that, the laminate for the inner layer, on which the green sheets for the outer ceramic layer are stacked, is pressed in the stacking direction by a hydrostatic press or a rigid press, and then cut along cutting lines parallel to the length and width directions to obtain a predetermined product size. The cross-sections in the thickness direction on both sides of the width direction formed by the cutting become the end faces at both ends of the internal electrode layer in the width direction W. Green sheets for the side ceramic parts are attached to the sides where the internal electrode layer is exposed, located on both sides in the width direction. In this way, an unfired laminate that will become the laminate 110 of the multilayer ceramic capacitor 100 is formed. Two or more green sheets for the outer ceramic layer may be stacked above and below the laminate for the inner layer, sandwiching it in between. Two or more green sheets for the side ceramic parts may be attached to the sides where the internal electrode layer is exposed, located on both sides in the width direction.

[0074] The unfired laminate is degreased and then N ２ In an atmosphere, the laminate is heat-treated at a predetermined temperature, and the binder is burned off. After that, the unfired laminate is N ２ -H ２ -H ２ The product is heated to the firing temperature in a reducing atmosphere consisting of oxygen gas, for example, at a heating rate of 500°C / min or more, and then fired. The firing temperature may be, for example, 1100°C to 1300°C.

[0075] Next, an annealing treatment is performed. The annealing treatment is preferable to the firing treatment as it has a lower maximum temperature and is performed in a weakly reducing atmosphere. The green sheets and conductive paste film for the internal ceramic layer, external ceramic layer, and side ceramic portion are as follows: the green sheet for the internal ceramic layer becomes the internal ceramic layer 130, the green sheet for the external ceramic layer becomes the external ceramic layer 160, the green sheet for the side ceramic portion becomes the side ceramic portion 170, and the conductive paste film becomes the internal electrode layer 140.

[0076] Next, after a base electrode layer is formed on the surface of the laminate 110, a plating layer is formed by electroplating so as to cover the base electrode layer.

[0077] The multilayer ceramic capacitor 100 is manufactured through the above series of processes.

[0078] The dimensions of the multilayer ceramic capacitor 100 are not particularly limited, but for example, the length L dimension may be 0.18 mm or more and 1.3 mm or less, the width W dimension may be 0.08 mm or more and 0.8 mm or less, and the stacking direction T dimension may be 0.08 mm or more and 0.8 mm or less.

[0079] The multilayer ceramic capacitor 100 may have a Vickers hardness of, for example, 1000 HV or more in the side ceramic portion, preferably 1200 HV or more, and more preferably 2000 HV or more. When the Vickers hardness is within the above range, cracking and chipping at the corners tend to be suppressed. The Vickers hardness is measured according to the method described in the Examples section below.

[0080] The multilayer ceramic capacitor 100 can be a two-terminal capacitor.

[0081] <Example 1> (Fabrication of green sheet for internal ceramic layer) BaTiO ３ By mixing this with oxides or carbonates of Dy, Mn, Ni, Si, and Al, a raw material powder for the internal ceramic layer was obtained. ３ The raw materials were blended so that, per 100 mol%, Dy was 1.5 mol% to 1.7 mol%, Mn was 0.1 mol% to 0.2 mol%, Ni was 1.3 mol% to 1.7 mol%, Si was 1.0 mol% to 1.4 mol%, and Al was 0.06 mol% to 0.1 mol%. The molar ratio (A / B) of the A-site component to the B-site component of the obtained raw material powder for the internal ceramic layer was in the range of 1.004 to 1.010. A green sheet for the internal ceramic layer was prepared using the raw material powder for the internal ceramic layer.

[0082] (Fabrication of green sheet for external ceramic layer) BaTiO ３ By mixing this with oxides or carbonates of Dy, Mn, Ni, Si, Al, and V, a raw material powder for the outer ceramic layer was obtained. ３The blend was formulated so that, per 100 mol%, Dy was at least 1.5 mol% and up to 1.7 mol%, Mn was at least 0.3 mol% and up to 0.9 mol%, Ni was at least 0.4 mol% and up to 0.6 mol%, Si was at least 1.1 mol% and up to 2.5 mol%, Al was at least 0.12 mol% and up to 0.25 mol%, and V was at least 0.03 mol% and up to 0.07 mol%, with the relationship between the Si, Al, and Mn content being Si > Mn > Al. Furthermore, the blend was formulated so that the Si content in the raw material powder for the outer ceramic layer was higher than the Si content in the raw material powder for the inner ceramic layer, the Al content in the raw material powder for the outer ceramic layer was higher than the Al content in the raw material powder for the inner ceramic layer, and the Mn content in the raw material powder for the outer ceramic layer was higher than the Mn content in the raw material powder for the inner ceramic layer. The molar ratio (A / B) of the A-site component to the B-site component of the obtained raw material powder for the outer ceramic layer was within the range of 1.004 to 1.010. A green sheet for the outer ceramic layer was prepared using the raw material powder for the outer ceramic layer.

[0083] (Preparation of green sheet for side ceramic section) A green sheet for the side ceramic section was prepared using the same raw material powder for the internal ceramic layer as the raw material powder for the external ceramic layer described above.

[0084] (Manufacturing of Multilayer Ceramic Capacitors) An internal electrode pattern was formed by printing a conductive paste mainly composed of Ni for the internal electrodes onto a green sheet for the internal ceramic layer in a predetermined pattern. Next, a predetermined number of green sheets for the external ceramic layer were stacked, and 550 green sheets for the internal ceramic layer with the internal electrode pattern printed on them were stacked on top of that, and then a predetermined number of green sheets for the external ceramic layer were stacked on top of that. After that, a stacked block was made by pressing in the stacking direction using an isostatic press. The stacked block was cut to a predetermined size, and a stacked chip was cut out. Two green sheets for the side ceramic parts were attached to each side of the stacked chip. At this time, the corners and edges of the stacked chip were rounded by barrel polishing. The stacked chip was sintered to make a stacked body. The sintering temperature was 1200°C, and the heating rate from the start of sintering to reaching the sintering temperature was 500°C / min or more. A conductive paste mainly composed of Cu for the external electrodes was applied to both end faces of the stacked chip, and the external electrode baked layer was formed by baking. A multilayer ceramic capacitor was obtained by applying Ni plating and Sn plating to the surface of the baked layer. The dimensions of the multilayer ceramic capacitor were within the range of 0.5 mm to 0.6 mm in the stacking direction, 0.5 mm to 0.6 mm in the width direction, and 1.0 mm to 1.1 mm in the length direction. The thickness of the outer ceramic layer was 35 μm, the thickness of the inner ceramic layer was 0.5 μm, the thickness of the side ceramic portion was 18 μm, and the thickness of the inner electrode layer was 0.45 μm. In addition, the amount of recess at the corners was 1 μm or less.

[0085] <Example 2, Comparative Examples 1 and 2> The multilayer ceramic capacitors of Example 2 and Comparative Examples 1 and 2 were manufactured by appropriately modifying the manufacturing conditions of Example 1 so that the pore ratio of the corners after firing was the value shown in Table 1.

[0086] (Measurement of Vickers Hardness) Five samples each of the multilayer ceramic capacitors in the examples and comparative examples were prepared, and the hardness of the ceramic surface on both sides of the multilayer ceramic capacitors was measured using a Vickers hardness tester, and the average value was calculated. The measurement conditions for Vickers hardness were: measurement load: 1000 gf, bottom dead center holding time: 10 s. When the Vickers hardness is 1000 HV or higher, cracking and chipping tend to be suppressed. The results are shown in Table 1.

[0087] (Measurement of Pore Ratio) The pore area ratio near the surface of the side ceramic portion of each sample of the multilayer ceramic capacitors in the examples and comparative examples was calculated. A cross-section parallel to the width direction W and the stacking direction T of the multilayer ceramic capacitor was imaged using a SEM. In the SEM image, the area enclosed by a first extension line E1 extending in the stacking direction along the side of the inner layer, a second extension line E2 extending in the width direction along the outermost inner electrode layer on the outer ceramic layer side of the inner layer, and a contour line E3 on the surface side of the side ceramic portion was defined as the corner. The corner was divided into a surface side and an inner layer side, and the fields of view on the surface side and the inner layer side were observed along a straight line E5 connecting the intersection of the first extension line E1 and the second extension line E2 to a point on the contour line E3 at an angle of 45°. Figure 8 schematically shows the observed fields of view on the surface side and the inner layer side. In Figure 8, the fields of view are shown schematically, so the scale of the SEM image and the size of the fields of view shown in Figure 8 do not match. The size of one field of view was 13 μm × 9 μm.

[0088] Image processing was applied to the captured images to measure the pore area. The pore area ratio was calculated by dividing this pore area by the area of ​​the multilayer ceramic capacitor visible in the captured image. The results are shown in Table 1. The pore ratio of the side ceramic portion was also measured, and it was confirmed that the pore ratio of the side ceramic portion and the corner portion were equivalent for both the example and comparative example multilayer ceramic capacitors.

[0089]

[0090] Since the pore ratio at the corners is the same as that of the side ceramic portion, it can be inferred that the Vickers hardness at the corners is also the same as that of the side ceramic portion. It is understood that the multilayer ceramic capacitor according to this disclosure has high Vickers hardness at the corners, thus suppressing cracking and chipping. Furthermore, in the multilayer ceramic capacitors of Examples 1 and 2, the pore ratio on the inner layer side of the corners is higher than that on the surface side of the corners, so that not only is there good moisture resistance and hardness, but crack propagation can also be effectively suppressed.

[0091] In the description of the embodiments described above, the combinable configurations may be combined with each other.

[0092] The embodiments disclosed herein should be considered in all respects to be illustrative and not restrictive. The scope of the invention is indicated by the claims rather than by the foregoing description, and all modifications within the meaning and scope of equivalents of the claims are intended.

[0093] Those skilled in the art will understand that the above-described exemplary embodiments are specific examples of the following embodiments.

[0094] [1] A multilayer ceramic capacitor comprising: an inner layer portion in which an inner ceramic layer and an inner electrode layer are alternately stacked; an outer ceramic layer disposed on both sides of the stacking direction of the inner layer portion; and a side ceramic portion disposed on both sides of the width direction perpendicular to the stacking direction of the inner layer portion and the outer ceramic layer, wherein the thickness of the side ceramic portion is 20 μm or less; and in a cross section of the laminate parallel to the width direction and the stacking direction, a corner portion is defined as the region enclosed by a first extension line extending in the stacking direction along the side of the inner layer portion, a second extension line extending in the width direction along the surface of the outermost inner electrode layer in the inner layer portion on the outer ceramic layer side, and the contour line on the surface side of the side ceramic portion, and when the corner portion is divided into a surface side and an inner layer portion side, the pore ratio on the surface side of the corner portion is 0.50% or less, and the pore ratio on the inner layer portion side of the corner portion is higher than the pore ratio on the surface side of the corner portion. [2] The multilayer ceramic capacitor according to [1], wherein the surface side and the inner layer side of the corner are demarcated by a curve formed by connecting the midpoints of straight lines that connect the intersection of the first extension line and the second extension line to a point on the contour line. [3] The multilayer ceramic capacitor according to [1] or [2], wherein, in the cross-section, when the region other than the corner of the outer ceramic layer and the side ceramic portion is demarcated into a surface side and an inner layer side, the pore ratio of the surface side of the region other than the corner is 3.0% or less. [4] The multilayer ceramic capacitor according to any one of [1] to [3], wherein the pore ratio of the effective side of the region other than the corner is higher than that of the surface side of the region other than the corner. [5] The multilayer ceramic capacitor according to any one of [1] to [4], wherein the inner ceramic layer, the outer ceramic layer and the side ceramic portion further contain manganese, and the manganese content of the outer ceramic layer and the side ceramic portion is greater than the manganese content of the inner ceramic layer. [6] The multilayer ceramic capacitor according to any one of [1] to [5], wherein the internal ceramic layer, the external ceramic layer, and the side ceramic portion further contain silicon, and the silicon content of the external ceramic layer and the side ceramic portion is greater than the silicon content of the internal ceramic layer.[7] The multilayer ceramic capacitor according to any one of [1] to [6], wherein the internal ceramic layer, the external ceramic layer, and the side ceramic portion further contain aluminum, and the aluminum content of the external ceramic layer and the side ceramic portion is greater than the aluminum content of the internal ceramic layer. [8] The multilayer ceramic capacitor according to any one of [1] to [7], wherein the thickness of the external ceramic layer is 40 μm or less. [9] The multilayer ceramic capacitor according to any one of [1] to [8], wherein the internal ceramic layer contains a plurality of grains, and when the particle size that accounts for 50% of the area-equivalent diameter of the plurality of grains is defined as D50, D50 is 80 nm or more and 140 nm or less.

[10] The multilayer ceramic capacitor according to any one of [1] to [9], wherein the external ceramic layer contains a plurality of grains, and when the particle size that accounts for 50% of the area-equivalent diameter of the plurality of grains contained in the external ceramic layer is defined as D50, D50 of the plurality of grains contained in the external ceramic layer is 180 nm or more and 360 nm or less.

[11] The multilayer ceramic capacitor according to any one of [1] to

[10] , wherein the side ceramic portion contains a plurality of grains, and when the particle size that accounts for 50% of the area circle equivalent diameter of the plurality of grains contained in the side ceramic portion is defined as D50, the D50 of the plurality of grains contained in the side ceramic portion is 180 nm or more and 360 nm or less.

[12] The multilayer ceramic capacitor according to any one of [1] to

[11] , wherein the amount of recess on the surface of the corner portion is 1 μm or less.

[13] The multilayer ceramic capacitor according to any one of [1] to

[12] , wherein the outer ceramic layer and the side ceramic portion further contain vanadium.

[0095] 100 Multilayer ceramic capacitor, 110 Laminate, 120 External electrode, 120A First external electrode, 120B Second external electrode, 130 Internal ceramic layer, 140 Internal electrode layer, 140A First internal electrode layer, 140B Second internal electrode layer, 140S Internal electrode layer, 150 Inner layer, 150A Region near the external ceramic layer, 150B Central region, 150C Region near the side ceramic part, 151 Side of the inner layer, 152 Surface on the external ceramic layer side, 160 External ceramic layer, 160A First external ceramic layer, 160B Second external ceramic layer, 161 First main surface, 162 Second main surface, 170 Side ceramic part, 170A First side ceramic part, 170B Second side ceramic part, 171 First side, 172 Second side, 180 End face ceramic part, 180A First end face ceramic portion, 180B; second end face ceramic portion, 181; first end face, 182; second end face.

Claims

1. A multilayer ceramic capacitor comprising: an inner layer portion in which an inner ceramic layer and an inner electrode layer are alternately stacked; an outer ceramic layer disposed on both sides of the stacking direction of the inner layer portion; and side ceramic portions disposed on both sides of the width direction perpendicular to the stacking direction of the inner layer portion and the outer ceramic layer, wherein the thickness of the side ceramic portion is 20 μm or less; and in a cross section of the laminate parallel to the width direction and the stacking direction, a corner portion is defined as the region enclosed by a first extension line extending in the stacking direction along the side of the inner layer portion, a second extension line extending in the width direction along the surface of the outermost inner electrode layer in the inner layer portion on the outer ceramic layer side, and the contour line on the surface side of the side ceramic portion, and when the corner portion is divided into a surface side and an inner layer portion side, the pore ratio on the surface side of the corner portion is 0.50% or less, and the pore ratio on the inner layer portion side of the corner portion is higher than the pore ratio on the surface side of the corner portion.

2. The surface side and the inner layer side of the corner portion are demarcated by a curve formed by connecting the midpoints of the straight lines that connect the intersection of the first extension line and the second extension line to a point on the contour line, as described in claim 1.

3. In the cross-section, when the regions other than the corners of the outer ceramic layer and the side ceramic portion are divided into a surface side and an inner layer side, the pore ratio of the surface side of the regions other than the corners is 3.0% or less, as described in claim 1 or 2.

4. The pore ratio on the effective portion side of the region other than the corner is higher than that on the surface side of the region other than the corner, according to any one of claims 1 to 3.

5. The multilayer ceramic capacitor according to any one of claims 1 to 4, wherein the internal ceramic layer, the external ceramic layer, and the side ceramic portion further contain manganese, and the manganese content of the external ceramic layer and the side ceramic portion is greater than the manganese content of the internal ceramic layer.

6. The multilayer ceramic capacitor according to any one of claims 1 to 5, wherein the internal ceramic layer, the external ceramic layer, and the side ceramic portion further contain silicon, and the silicon content of the external ceramic layer and the side ceramic portion is greater than the silicon content of the internal ceramic layer.

7. The multilayer ceramic capacitor according to any one of claims 1 to 6, wherein the internal ceramic layer, the external ceramic layer, and the side ceramic portion further contain aluminum, and the aluminum content of the external ceramic layer and the side ceramic portion is greater than the aluminum content of the internal ceramic layer.

8. The multilayer ceramic capacitor according to any one of claims 1 to 7, wherein the thickness of the outer ceramic layer is 40 μm or less.

9. The multilayer ceramic capacitor according to any one of claims 1 to 8, wherein the internal ceramic layer comprises a plurality of grains, and in the particle size distribution of the plurality of grains with an area circle equivalent diameter, when the particle size that accounts for 50% of the cumulative area is defined as D50, D50 is 80 nm or more and 140 nm or less.

10. The multilayer ceramic capacitor according to any one of claims 1 to 9, wherein the outer ceramic layer contains a plurality of grains, and when the particle size that accounts for 50% of the area circle equivalent diameter of the plurality of grains contained in the outer ceramic layer is defined as D50, the D50 of the plurality of grains contained in the outer ceramic layer is 180 nm or more and 360 nm or less.

11. The multilayer ceramic capacitor according to any one of claims 1 to 10, wherein the side ceramic portion contains a plurality of grains, and when the particle size that accounts for 50% of the area circle equivalent diameter of the plurality of grains contained in the side ceramic portion is defined as D50, the D50 of the plurality of grains contained in the side ceramic portion is 180 nm or more and 360 nm or less.

12. The amount of recess on the surface of the corner portion is 1 μm or less, according to any one of claims 1 to 11.

13. The multilayer ceramic capacitor according to any one of claims 1 to 12, wherein the outer ceramic layer and the side ceramic portion further contain vanadium.

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