Laminated capacitor

Abstract

To provide a laminated capacitor which has improved electrode connection and is excellent in reliability.SOLUTION: A laminated capacitor includes a capacitor body including a dielectric layer and an internal electrode, and an external electrode disposed outside the capacitor body. The internal electrode includes zirconium (Zr). An average content of the zirconium (Zr) relative to the whole internal electrode is 0.0005 mole% or larger and below 5.0 mole%. The dielectric layer includes a plurality of dielectric crystal grains. At least one or more of the plurality of dielectric crystal grains have core-shell structures, and the core, the shell or all of them contain zirconium (Zr).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a multilayer capacitor.

Background Art

[0002] Recently, as the multifunctionalization and miniaturization of electronic devices have advanced rapidly, the miniaturization and performance improvement of electronic components have also been progressing at a high speed. In addition, the requirements for high reliability of electrical devices used in automobiles or network facilities, etc., and electronic components for industrial use have also increased significantly.

[0003] In order to meet such market requirements, the competition in the technological development of manual components such as inductors, capacitors, or resistors has been accelerating. In particular, in the development of various products of multilayer ceramic capacitors (MLCCs), which are manual components with continuously increasing applications and usage amounts, many efforts are required to preempt the market.

[0004] In addition, a multilayer capacitor is a capacitor manufactured in a form in which dielectric layers and internal electrodes are stacked, and is used in various electronic devices such as mobile phones, notebook computers, and LCD TVs.

[0005] Recently, with the development of technology, multilayer capacitors are required to be miniaturized and have a higher capacitance. For this purpose, technical development has been carried out to increase the connectivity of the internal electrodes in contact with the dielectric layer to increase the effective electrode area, or to reduce the particle size of the dielectric material and the internal electrode material.

[0006] However, if the above materials are granulated, the melting point may decrease, and the thermal shrinkage start temperature of the materials may decrease. In particular, in the case of the metal material contained in the internal electrode, the rate of decrease in the thermal shrinkage start temperature is higher than that of the ceramic material contained in the dielectric layer, so that the difference in the thermal shrinkage temperature between the dielectric layer and the internal electrode becomes large.

[0007] The greater the difference in the thermal shrinkage temperature between the dielectric layer and the internal electrode, the greater the likelihood that the electrode connectivity will decrease after firing the dielectric layer and the internal electrode, and the electrical capacitance and reliability of the multilayer capacitor may deteriorate.

[0008] Currently, in order to reduce the difference in the thermal shrinkage temperature between the dielectric layer and the internal electrode, a method of adding a nano-sized barium titanate (BaTiO3) co-material during the manufacture of the internal electrode is used.

[0009] However, if the content of the barium titanate co-material increases, the film density of the internal electrode decreases, and a side effect occurs in which the co-material diffused into the dielectric layer during the firing process increases the thickness of the dielectric layer and decreases the capacitance of the capacitor. Therefore, there is a situation where the development of a new co-material that has high thermal stability and does not cause side effects even when diffused into the dielectric layer is required.

Summary of the Invention

Problems to be Solved by the Invention

[0010] One aspect of the embodiment provides a multilayer capacitor with improved electrode connectivity and excellent reliability.

[0011] However, the problems to be solved by the embodiment are not limited to the above problems, and can be variously extended within the scope of the technical idea included in the embodiment.

Means for Solving the Problems

[0012] A multilayer capacitor according to an embodiment includes a capacitor body including a dielectric layer and an internal electrode, and an external electrode disposed outside the capacitor body, the internal electrode includes zirconium (Zr), and an average content of the zirconium (Zr) with respect to the entire internal electrode is 0.0005 mol% or more and less than 5.0 mol%, the dielectric layer includes a plurality of dielectric crystallites, at least one or more of the plurality of dielectric crystallites have a core-shell structure, and the core, the shell, or all of them include zirconium (Zr).

[0013] The internal electrode can contain a conductive metal and the zirconium (Zr).

[0014] The dielectric crystal grains contain a main component and a sub-component, and the main component is Ba m TiO3 (0.995 ≦ m ≦ 1.010), (Ba 1-x Ca x ) m (Ti 1-y Zr y )O3 (0.995 ≦ m ≦ 1.010, 0 ≦ x ≦ 0.10, 0 < y ≦ 0.20), Ba m (Ti 1-x Zr x )O3 (0.995 ≦ m ≦ 1.010, x ≦ 0.10), (Ba 1-x Ca x ) m (Ti 1-y Sn y )O3 (0.995 ≦ m ≦ 1.010, 0 ≦ x ≦ 0.10, 0 < y ≦ 0.20), or a combination thereof can be included.

[0015] The sub-component can contain zirconium (Zr), manganese (Mn), chromium (Cr), silicon (Si), aluminum (Al), magnesium (Mg), tin (Sn), antimony (Sb), hafnium (Hf), germanium (Ge), gallium (Ga), indium (In), lanthanum (La), yttrium (Y), actinium (Ac), 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), lutetium (Lu), or a combination thereof.

[0016] The average content of the zirconium (Zr) with respect to the entire internal electrode may be 0.001 mol% to 1.0 mol%.

[0017] The average content of zirconium (Zr) in the shell relative to the entire shell may be greater than the average content of zirconium (Zr) in the core relative to the entire core.

[0018] The average content of zirconium (Zr) in the shell relative to the entire shell may be 0.001 mol% to 10.0 mol%.

[0019] The average content of zirconium (Zr) in the core relative to the entire core may be 0 mol% to 2.0 mol%.

[0020] The average thickness of the dielectric layer may be 0.1 μm to 5 μm.

[0021] The average thickness of the internal electrode may be 0.1 μm to 2 μm.

[0022] A multilayer capacitor according to another embodiment includes a capacitor body including a dielectric layer and an internal electrode, and an external electrode disposed outside the capacitor body. The internal electrode includes a conductive metal and zirconium (Zr), and the average content of zirconium (Zr) relative to the entire internal electrode is 0.0005 mol% or more and less than 5.0 mol%. The dielectric layer includes a plurality of dielectric crystallites, and at least one or more of the plurality of dielectric crystallites have a core-shell structure, and the core, the shell, or all of them include zirconium (Zr).

[0023] The dielectric crystallites include a main component and a sub-component, and the main component is Ba m TiO3 (0.995 ≦ m ≦ 1.010), (Ba 1-x Ca x ) m (Ti 1-y Zr y )O3 (0.995 ≦ m ≦ 1.010, 0 ≦ x ≦ 0.10, 0 < y ≦ 0.20), Ba m (Ti 1-x Zr x )O3 (0.995 ≦ m ≦ 1.010, x ≦ 0.10), (Ba 1-x Cax ) m (Ti 1-y Sn y )O3 (0.995 ≦ m ≦ 1.010, 0 ≦ x ≦ 0.10, 0 < y ≦ 0.20), or combinations thereof can be included.

[0024] The sub-components may include zirconium (Zr), manganese (Mn), chromium (Cr), silicon (Si), aluminum (Al), magnesium (Mg), tin (Sn), antimony (Sb), hafnium (Hf), germanium (Ge), gallium (Ga), indium (In), lanthanum (La), yttrium (Y), actinium (Ac), 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), lutetium (Lu), or combinations thereof.

[0025] The average content of zirconium (Zr) with respect to the entire internal electrode may be 0.001 mol% to 1.0 mol%.

[0026] The average content of zirconium (Zr) in the shell with respect to the entire shell may be greater than the average content of zirconium (Zr) in the core with respect to the entire core.

[0027] The average content of zirconium (Zr) in the shell with respect to the entire shell may be 0.001 mol% to 10.0 mol%.

[0028] The average content of zirconium (Zr) in the core with respect to the entire core may be 0 mol% to 2.0 mol%.

[0029] The average thickness of the dielectric layer may be 0.1 μm to 5 μm.

[0030] The average thickness of the internal electrode may be 0.1 μm to 2 μm.

Advantages of the Invention

[0031] According to the multilayer capacitor according to the embodiment, there is an advantage that the electrode connectivity is improved and the reliability is excellent.

[0032] However, the various and beneficial advantages and effects of the present invention are not limited to the above-described content, and should be more easily understood in the process of explaining the specific embodiments of the present invention.

Brief Description of the Drawings

[0033]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Modes for Carrying Out the Invention

[0034] Hereinafter, embodiments of the present invention will be described in detail so that those having ordinary knowledge in the technical field to which the present invention pertains can easily implement it with reference to the attached drawings. In order to clearly explain the present invention in the drawings, parts unnecessary for the explanation are omitted, and the same reference numerals are given to the same or similar components throughout the specification. Also, the attached drawings are merely for facilitating the understanding of the embodiments disclosed in this specification, and the technical idea disclosed in this specification is not limited by the attached drawings, and it must be understood that all changes, equivalents, and alternatives included in the idea and technical scope of the present invention are included.

[0035] Terms including ordinal numbers such as first, second, etc. can be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another.

[0036] When a certain component is referred to as being "connected to" or "attached to" another component, it should be understood that it may be directly connected to, attached to, or opposed to the other component, but there may also be other components in between. On the contrary, when a certain component is referred to as being "directly connected to" or "directly attached to" another component, it should be understood that there are no other components in between.

[0037] Throughout the specification, terms such as "including" or "having" are intended to specify the presence of the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and it should not be understood that the presence or addition possibility of one or more other features, numbers, steps, operations, components, parts, or combinations thereof is excluded in advance. Therefore, when a certain part "includes" a certain component, this means that it can further include other components rather than excluding other components unless otherwise stated to the contrary.

[0038] FIG. 1 is a perspective view showing a multilayer capacitor 100 according to an embodiment, FIG. 2 is a cross-sectional view of the multilayer capacitor 100 cut along the line I-I' of FIG. 1, and FIG. 3 is an exploded perspective view showing the laminated structure of internal electrodes in the capacitor body 110 of FIG. 1.

[0039] To clearly explain this embodiment, if directions are defined, the L-axis, W-axis, and T-axis shown in the drawings respectively indicate the length direction, width direction, and thickness direction of the capacitor body 110. Here, the thickness direction (T-axis direction) may be a direction perpendicular to the wide surface (main surface) of the sheet-shaped component, and as an example, it can be used as the same concept as the lamination direction in which the dielectric layer 111 is laminated. The length direction (L-axis direction) may be a direction that extends parallel to the wide surface (main surface) of the sheet-shaped component and is substantially perpendicular to the thickness direction (T-axis direction), and as an example, it may be the direction in which the first external electrode 131 and the second external electrode 132 are located on both sides. The width direction (W-axis direction) may be a direction that extends parallel to the wide surface (main surface) of the sheet-shaped component and is substantially perpendicular to the thickness direction (T-axis direction) and the length direction (L-axis direction), and the length in the length direction (L-axis direction) of the sheet-shaped component may be even longer than the length in the width direction (W-axis direction).

[0040] Referring to FIGS. 1 to 3, a multilayer capacitor 100 according to an embodiment can include a capacitor body 110, and a first external electrode 131 and a second external electrode 132 disposed at both ends facing the length direction (L-axis direction) of the capacitor body 110.

[0041] The capacitor body 110 may be, as an example, a roughly hexahedral shape.

[0042] In this embodiment, for convenience of explanation, both surfaces of the capacitor body 110 that face each other in the thickness direction (T-axis direction) are defined as the first surface and the second surface, both surfaces that are connected to the first surface and the second surface and face each other in the length direction (L-axis direction) are defined as the third surface and the fourth surface, and both surfaces that are connected to the first surface and the second surface, connected to the third surface and the fourth surface, and face each other in the width direction (W-axis direction) are defined as the fifth surface and the sixth surface.

[0043] As an example, the first surface, which is the lower surface, can be the surface facing the mounting direction. Also, the first to sixth surfaces may be flat, but the present embodiment is not limited thereto. For example, the first to sixth surfaces may be curved surfaces with a convex central portion, and the corners that are the boundaries of each surface may be rounded.

[0044] The shape, dimensions, and the number of stacked dielectric layers 111 of the capacitor body 110 are not limited to those shown in the drawings of the present embodiment.

[0045] The capacitor body 110 is formed by stacking a plurality of dielectric layers 111 in the thickness direction (T-axis direction) and then firing, and includes a plurality of dielectric layers 111, and a first internal electrode layer 121 and a second internal electrode layer 122 that are alternately arranged in the thickness direction (T-axis direction) with the dielectric layer 111 interposed therebetween.

[0046] At this time, the boundaries between the respective adjacent dielectric layers 111 of the capacitor body 110 can be integrated to such an extent that they are difficult to confirm without using a scanning electron microscope (SEM).

[0047] Also, the capacitor body 110 can include an active region and cover regions 112 and 113.

[0048] The active region is a portion that contributes to the formation of the capacitance of the multilayer capacitor 100. As an example, the active region may be a region where the first internal electrode layer 121 or the second internal electrode layer 122 stacked along the thickness direction (T-axis direction) overlaps.

[0049] The cover regions 112 and 113 are margin portions in the thickness direction and can be respectively arranged on the first surface and the second surface sides of the active region in the thickness direction (T-axis direction). Such cover regions 112 and 113 may be a single dielectric layer 111 or two or more dielectric layers 111 laminated on the upper surface and the lower surface of the active region, respectively.

[0050] Also, the capacitor body 110 can further include side cover regions. The side cover regions are margin portions in the width direction and can be respectively arranged on the fifth surface and the sixth surface sides of the active region in the width direction (W-axis direction). Such side cover regions can be formed by applying a conductive paste layer for forming an internal electrode layer only on a partial region of the surface of the dielectric green sheet when applying the conductive paste layer on the surface of the dielectric green sheet, laminating dielectric green sheets on both side surfaces of the surface of the dielectric green sheet where the conductive paste layer is not applied, and then firing.

[0051] The cover regions 112 and 113 and the side cover regions serve to prevent damage to the first internal electrode layer 121 and the second internal electrode layer 122 due to physical or chemical stress.

[0052] Internal electrode The first internal electrode 121 and the second internal electrode 122 are electrodes having different polarities from each other, and are alternately arranged facing each other along the T-axis direction with the dielectric layer 111 interposed therebetween, and one end of each is exposed through the third surface and the fourth surface of the capacitor body 110.

[0053] The first internal electrode 121 and the second internal electrode 122 are electrically insulated from each other by the dielectric layer 111 disposed therebetween.

[0054] The ends of the first internal electrode 121 and the second internal electrode 122 alternately exposed through the third surface and the fourth surface of the capacitor body 110 are respectively connected to the first external electrode 131 and the second external electrode 132 and can be electrically connected.

[0055] The internal electrodes 121 and 122 contain zirconium (Zr). As an example, they can contain a conductive metal and zirconium (Zr), and can contain an alloy of a conductive metal and zirconium (Zr).

[0056] Zirconium (Zr) can be added to the conductive paste for the internal electrode in the form of Zr oxide (ZrO2). After going through the firing process, the internal electrodes 121 and 122 can contain Zr oxide (ZrO2), Zr, or a combination thereof.

[0057] Since the melting point of Zr oxide (ZrO2) is about 1100 °C higher than that of barium titanate (BaTiO3), which was a conventionally used co-material, when Zr oxide is included in the conductive paste for the internal electrode and fired, the thermal shrinkage delay effect of the internal electrode is very excellent compared to the case of using barium titanate. Thereby, the thermal stability of the internal electrode is increased, and the electrode connectivity of the internal electrode can be greatly improved. If the electrode connectivity is improved, there is an advantage that the capacitance and BDV (Break Down Voltage) of the multilayer capacitor can be increased.

[0058] As an example, the conductive metal can further contain metals such as Ni, Cu, Ag, Pd, or Au, or alloys thereof, such as an Ag-Pd alloy. As an example, when the conductive metal is Ni, the first internal electrode 121 and the second internal electrode 122 contain Ni and Zr, and can contain an Ni-Zr alloy as an example.

[0059] Also, the first internal electrode 121 and the second internal electrode 122 can contain dielectric particles of the same composition system as the ceramic material contained in the dielectric layer 111.

[0060] The first internal electrode 121 and the second internal electrode 122 can be formed using a conductive paste containing a conductive metal. As the printing method of the conductive paste, a screen printing method, a gravure printing method, or the like can be used.

[0061] In one embodiment, the average content of zirconium (Zr) with respect to the entire internal electrodes 121 and 122 is 0.0005 mol% or more and less than 5.0 mol%.

[0062] As an example, the average content of zirconium (Zr) with respect to the entire internal electrodes 121 and 122 may be 0.0005 mol% or more or 0.001 mol% or more, and may be less than 5 mol%, 2.5 mol% or less, or 1.0 mol% or less.

[0063] As an example, the average content of zirconium (Zr) with respect to the entire internal electrodes 121 and 122 may be 0.0005 mol% to 2.5 mol%, for example, 0.001 mol% to 2.5 mol%, or 0.001 mol% to 1.0 mol%.

[0064] When the average content of zirconium (Zr) in the internal electrodes 121 and 122 is less than 0.0005 mol%, the effect of improving electrode connectivity may be negligible, and when it is 5 mol% or more, the electrical characteristics and reliability of the capacitor may deteriorate.

[0065] FIG. 4 is a SEM (Scanning Electron Microscope) image of a part of the cross-section of a multilayer capacitor according to one embodiment, and FIG. 5 is an image showing a part of the SEM image of FIG. 4 mapped with a Zr component.

[0066] Referring to FIGS. 4 and 5, the average content (mol%) of zirconium (Zr) in the internal electrodes 121 and 122 can be measured by the following method.

[0067] First, after placing the multilayer capacitor 100 in an epoxy mixture and curing it, polish the sides of the capacitor body 110 in the W-axis direction and the T-axis direction to the 1 / 2 point in the L-axis direction, maintain it in a vacuum atmosphere chamber after fixing, and prepare a cross-sectional sample (hereinafter referred to as "cross-sectional sample") cut from the center of the capacitor body 110 in the L-axis direction in the W-axis direction and the T-axis direction.

[0068] After that, prepare an SEM image or a TEM image obtained by observing the cross-sectional sample with a scanning electron microscope (SEM) or a transmission electron microscope (TEM).

[0069] As an example, prepare an SEM image as shown in FIG. 4, map it with the Zr component as shown in FIG. 5, and confirm the position where Zr is distributed in the cross-sectional sample. Also, the content of Zr can be derived through SEM-EDAX or TEM-EDAX quantitative analysis.

[0070] Select the internal electrode located at the central part of the cross-sectional sample, derive the content of Zr through SEM-EDAX or TEM-EDAX quantitative analysis at at least three or more points of the selected internal electrode, and then calculate the arithmetic mean value to derive the average content of Zr contained in the internal electrode.

[0071] As an example, the average thickness of the first internal electrodes 121 and 122 may be 0.1 μm or more, 0.2 μm or more, or 0.5 μm or more, and may also be 2.0 μm or less, 1.5 μm or less, or 1.0 μm or less.

[0072] The average thickness of the first internal electrodes 121 and 122 can be measured by the following method.

[0073] In the scanning electron microscope (SEM) image of the cross-sectional sample, taking the central point in the L-axis direction or W-axis direction of the first internal electrode 121 or the second internal electrode 122 as the reference point, the arithmetic mean value of the thicknesses of the first internal electrodes 121 and 122 at 10 points separated from the reference point by a predetermined interval can be obtained, and the average thickness of the internal electrode can be obtained.

[0074] The interval between the 10 points can be adjusted according to the scale of the scanning electron microscope (SEM) image. For example, the interval can be 1 μm to 100 μm, 1 μm to 50 μm, or 1 μm to 10 μm.

[0075] At this time, all 10 points must be located within the first internal electrode 121 or the second internal electrode 122. If all 10 points are not located within the first internal electrode 121 or the second internal electrode 122, the position of the reference point can be changed, or the interval between the 10 points can be adjusted.

[0076] Dielectric layer The Zr oxide (ZrO2) added to the conductive paste for the internal electrode partially diffuses into the dielectric layer 111 in the form of Zr through the firing process, and the diffused Zr is mainly arranged on the shell of the dielectric crystal grains having a core-shell structure. As a result, the insulation characteristics of the dielectric layer are increased, and the reliability of the multilayer capacitor can be significantly improved.

[0077] The dielectric layer 111 includes a plurality of dielectric crystal grains.

[0078] The dielectric crystal grains include a main component and a sub-component.

[0079] The main component is the base material of the dielectric, has a high dielectric constant, and contributes to the formation of the dielectric constant of the multilayer capacitor 100.

[0080] The main component is Ba m TiO3 (0.995 ≦ m ≦ 1.010), (Ba 1-x Ca x ) m (Ti 1-yZr y )O3 (0.995 ≤ m ≤ 1.010, 0 ≤ x ≤ 0.10, 0 < y ≤ 0.20), Ba m (Ti 1-x Zr x )O3 (0.995 ≤ m ≤ 1.010, x ≤ 0.10), (Ba 1-x Ca x ) m (Ti 1-y Sn y )O3 (0.995 ≤ m ≤ 1.010, 0 ≤ x ≤ 0.10, 0 < y ≤ 0.20), or a dielectric material containing a combination thereof may be used.

[0081] As a specific example, the main component may be (Ba 1-x Ca x ) m (Ti 1-y Zr y )O3 (0.995 ≤ m ≤ 1.010, 0 ≤ x ≤ 0.10, 0 < y ≤ 0.20), Ba m (Ti 1-x Zr x )O3 (0.995 ≤ m ≤ 1.010, x ≤ 0.10), or a combination thereof.

[0082] As an example, the main component may include BaTiO3, Ba(Ti,Zr)O3, Ba(Ti,Sn)O3, (Ba,Ca)TiO3, (Ba,Ca)(Ti,Zr)O3, (Ba,Ca)(Ti,Sn)O3, (Ba,Sr)TiO3, (Ba,Sr)(Ti,Zr)O3, (Ba,Sr)(Ti,Sn)O3, or a combination thereof.

[0083] The secondary components can include zirconium (Zr), manganese (Mn), chromium (Cr), silicon (Si), aluminum (Al), magnesium (Mg), tin (Sn), antimony (Sb), hafnium (Hf), germanium (Ge), gallium (Ga), indium (In), lanthanum (La), yttrium (Y), actinium (Ac), 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), lutetium (Lu), or combinations thereof.

[0084] The dielectric layer 111 can further include a ceramic additive, an organic solvent, a binder, a dispersant, or combinations thereof.

[0085] In one embodiment, at least one or more of the plurality of dielectric crystallites can have a core-shell structure.

[0086] A dielectric crystallite having a core-shell structure includes a dielectric core and a shell surrounding at least a part of the core within one dielectric crystallite.

[0087] The core and the shell have different molar ratios of the secondary component to the main component. For example, the molar ratio of the secondary component to the main component can change abruptly at the boundary between the core and the shell. Thereby, the boundary between the core and the shell can be easily distinguished and this can be confirmed through transmission electron microscopy - energy dispersive X-ray analysis (TEM-EDX).

[0088] As an example, no secondary component or only a trace amount of the secondary component is present in the core. Therefore, the core consists of only a pure main component without impurities, and the pure main component can generally have a higher dielectric constant than the main component doped with impurity elements. Thereby, the core can play a role in maintaining the dielectric constant.

[0089] The shell contains more secondary components than the core. The secondary component doped at the B-site of the main component (perovskite ABO3 structure) in the shell has the effect of increasing the band gap energy for other rare earths and doping elements to diffuse into the dielectric crystal grains. Thus, it can serve as a barrier to suppress the diffusion of other rare earths and doping elements into the dielectric crystal grains. The shell can play a role in suppressing the growth of dielectric crystal grains and contribute to the refinement of dielectric crystal grains. In addition, the secondary component doped at the A-site of the main component in the shell can play a role in improving the reliability and dielectric constant.

[0090] As an example, the average area of the core contained in one dielectric crystal grain may be 50% - 90%, for example, 60% - 90%, or 70% - 90%.

[0091] As an example, the average area of the shell contained in one dielectric crystal grain may be 10% - 50%, for example, 10% - 40%, or 10% - 30%.

[0092] In one embodiment, the core, the shell, or all of them contain zirconium (Zr).

[0093] In one embodiment, the average content of zirconium (Zr) in the shell with respect to the whole shell may be greater than the average content of zirconium (Zr) in the core with respect to the whole core.

[0094] In one embodiment, the average content of zirconium (Zr) in the shell with respect to the whole shell may be 0.001 mol% - 10.0 mol%, for example, 0.01 mol% - 10.0 mol%, 0.1 mol% - 10.0 mol%, or 0.1 mol% - 5.0 mol%.

[0095] In one embodiment, the average content of zirconium (Zr) contained in the core may be 0 mol% to 2.0 mol% based on the entire core, for example, 0 mol% to 1.0 mol%, or 0 mol% to 0.5 mol%.

[0096] When the average content of zirconium (Zr) contained in the core and the shell satisfies the above numerical range, a multilayer capacitor with excellent reliability can be realized.

[0097] FIG. 6 is a TEM (Transmission Electron Microscope) image of a part of the cross-section of a multilayer capacitor according to one embodiment, and FIG. 7 is an image showing a part of the TEM image of FIG. 6 mapped with a Zr component.

[0098] Referring to FIGS. 6 and 7, the average content of zirconium (Zr) contained in the core and the shell can be measured by the following method.

[0099] Select three or more dielectric crystallites located within about 200 nm from the interface between the internal electrode and the dielectric layer in the TEM image of the cross-section sample in the direction of the center of the dielectric layer. Using the results of mapping each selected dielectric crystallite with a Zr component, the boundary between the core and the shell is distinguished, and three points are selected in the core and shell regions respectively. After deriving the content of Zr through SEM-EDAX or TEM-EDAX quantitative analysis in the selected regions, the arithmetic mean value can be calculated to derive the average content of zirconium (Zr) contained in the core and the shell.

[0100] As an example, the average thickness of the dielectric layer 111 may be 0.1 μm or more, or 0.5 μm or more, and may be 5.0 μm or less, 2.5 μm or less, or 1.0 μm or less.

[0101] The average thickness of the dielectric layer 111 can be measured by the following method.

[0102] First, prepare a scanning electron microscope (SEM) image obtained by observing a cross-sectional sample with a scanning electron microscope.

[0103] In the scanning electron microscope (SEM) image of the cross-sectional sample, taking the central point in the L-axis direction or W-axis direction of the dielectric layer 111 as a reference point, the arithmetic mean value of the thickness of the dielectric layer 111 at 10 points separated from the reference point by a predetermined interval can be obtained, and it can be used as the average thickness of the dielectric layer 111.

[0104] The interval between the 10 points can be adjusted according to the scale of the scanning electron microscope (SEM) image, and for example, it may be an interval of 1 μm to 100 μm, 1 μm to 50 μm, or 1 μm to 10 μm.

[0105] At this time, all 10 points must be located within the dielectric layer 111. If all 10 points are not located within the dielectric layer 111, the position of the reference point can be changed, or the interval between the 10 points can be adjusted.

[0106] External electrode The first external electrode 131 and the second external electrode 132 are provided with voltages of different polarities and can be electrically connected by being respectively connected to the exposed portions of the first internal electrode 121 and the second internal electrode 122.

[0107] With the above configuration, when a predetermined voltage is applied to the first external electrode 131 and the second external electrode 132, charges are accumulated between the first internal electrode 121 and the second internal electrode 122 facing each other. At this time, the capacitance of the multilayer capacitor 100 becomes proportional to the overlapping area of the first internal electrode 121 and the second internal electrode 122 that overlap each other along the T-axis direction in the active region.

[0108] The first external electrode 131 and the second external electrode 132 are respectively disposed on the third surface and the fourth surface of the capacitor body 110 and connected to the first internal electrode 121 and the second internal electrode 122, and the first connection portion and the second connection portion, the third surface and the fourth surface of the capacitor body 110, and the first surface and the second surface or the fifth surface and the sixth surface of the capacitor body 110. Each may include a first band portion and a second band portion disposed at the corners where the surfaces are in contact.

[0109] The first band portion and the second band portion are respectively extended from the first connection portion and the second connection portion to a part of the first surface and the second surface or the fifth surface and the sixth surface of the capacitor body 110. The first band portion and the second band portion can play a role in improving the adhesion strength of the first external electrode 131 and the second external electrode 132.

[0110] As an example, the first external electrode 131 and the second external electrode 132 may each include a sintered metal layer in contact with the capacitor body 110, a conductive resin layer disposed to cover the sintered metal layer, and a plating layer disposed to cover the conductive resin layer.

[0111] The sintered metal layer can include a conductive metal and indium (In).

[0112] The sintered metal layer can include copper (Cu), nickel (Ni), silver (Ag), palladium (Pd), gold (Au), platinum (Pt), tin (Sn), tungsten (W), titanium (Ti), lead (Pb), alloys thereof, or combinations thereof as the conductive metal. For example, copper (Cu) can include a copper (Cu) alloy. As an example, when the conductive metal is Cu, the sintered metal layer includes Cu and In, and can include a Cu-In alloy as an example. Also, when the conductive metal includes copper, the metal other than copper may be included in an amount of 5 mol parts or less per 100 mol parts of copper.

[0113] As an example, the sintered metal layer can further contain glass. In this case, the sintered metal layer can contain a composition in which an oxide is mixed as the glass, and for example, it may be one or more selected from the group consisting of silicon oxide, boron oxide, aluminum oxide, transition metal oxide, alkali metal oxide, and alkaline earth metal oxide. The transition metal is selected from the group consisting of zinc (Zn), titanium (Ti), copper (Cu), vanadium (V), manganese (Mn), iron (Fe), and nickel (Ni), the alkali metal is selected from the group consisting of lithium (Li), sodium (Na), and potassium (K), and the alkaline earth metal may be one or more selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba).

[0114] Optionally, the conductive resin layer is formed on the sintered metal layer, and can be formed, for example, in a form that completely covers the sintered metal layer. On the other hand, the first external electrode 131 and the second external electrode 132 may not contain the sintered metal layer. In this case, the conductive resin layer can be in direct contact with the capacitor body 110.

[0115] The conductive resin layer extends to the first and second surfaces or the fifth and sixth surfaces of the capacitor body 110, and the length of the region (i.e., the band portion) where the conductive resin layer extends and is disposed on the first and second surfaces or the fifth and sixth surfaces of the capacitor body 110 may be longer than the length of the region (i.e., the band portion) where the sintered metal layer extends and is disposed on the first and second surfaces or the fifth and sixth surfaces of the capacitor body 110. That is, the conductive resin layer is formed on the sintered metal layer and can be formed in a form that completely covers the sintered metal layer.

[0116] The conductive resin layer contains resin and conductive metal.

[0117] The resin contained in the conductive resin layer is not particularly limited as long as it has bonding properties and shock absorbency and can be mixed with the conductive metal powder to make a paste. For example, it can contain a phenol resin, an acrylic resin, a silicon resin, an epoxy resin, or a polyimide resin.

[0118] The conductive metal contained in the conductive resin layer serves to be electrically connected to the first internal electrode 121 and the second internal electrode 122 or the sintered metal layer.

[0119] The conductive metal contained in the conductive resin layer can have a spherical, flake-shaped, or a combination of these forms. That is, the conductive metal may consist only of flake-shaped or only of spherical, or may be in a form in which flakes and spheres are mixed.

[0120] Here, the spherical shape can include forms that are not completely spherical. For example, it can include forms in which the length ratio of the major axis to the minor axis (major axis / minor axis) is 1.45 or less. The flake-shaped powder means a powder having a flat and elongated form, and is not particularly limited. For example, the length ratio of the major axis to the minor axis (major axis / minor axis) may be 1.95 or more.

[0121] The first external electrode 131 and the second external electrode 132 can further include a plating layer disposed outside the conductive resin layer.

[0122] The plating layer can include nickel (Ni), copper (Cu), tin (Sn), palladium (Pd), platinum (Pt), gold (Au), silver (Ag), tungsten (W), titanium (Ti), lead (Pb), etc., alone or alloys thereof. As an example, the plating layer may be a nickel (Ni) plating layer or a tin (Sn) plating layer, or may be in a form in which a nickel (Ni) plating layer and a tin (Sn) plating layer are sequentially laminated, or may be in a form in which a tin (Sn) plating layer, a nickel (Ni) plating layer, and a tin (Sn) plating layer are sequentially laminated. Also, the plating layer can include a plurality of nickel (Ni) plating layers and / or a plurality of tin (Sn) plating layers.

[0123] The plating layer can improve the mountability with the substrate of the multilayer capacitor 100, the structural reliability, the durability against the outside, the heat resistance, and the equivalent series resistance (ESR).

[0124] Manufacturing method of multilayer capacitor The manufacturing method of the multilayer capacitor according to another embodiment includes a step of manufacturing a capacitor body including a dielectric layer and an internal electrode, and a step of forming an external electrode on the outside of the capacitor body.

[0125] First, the manufacturing of the capacitor body will be described.

[0126] In the manufacturing process of the capacitor body, a dielectric paste that becomes a dielectric layer after firing and a conductive paste that becomes an internal electrode after firing are prepared.

[0127] The dielectric paste is manufactured, for example, in the following manner. Dielectric powder is uniformly mixed by means such as wet mixing, dried, and then heat-treated under predetermined conditions to obtain plastic powder. An organic vehicle or an aqueous vehicle is added to the obtained plastic powder and kneaded to prepare a dielectric paste.

[0128] The obtained dielectric paste is formed into a sheet by a technique such as the doctor blade method to obtain a dielectric green sheet. The dielectric paste may also contain additives selected from various dispersants, plasticizers, dielectrics, sub-component compounds, or glass as necessary.

[0129] The conductive paste for the internal electrode is prepared by kneading conductive powder made of a conductive metal or its alloy with a binder and a solvent. As an example, the conductive paste for the internal electrode can be prepared by kneading zirconium oxide. The conductive paste for the internal electrode may contain ceramic powder (for example, barium titanate powder) as a co-material as necessary. The co-material can function to suppress the sintering of the conductive powder during the firing process.

[0130] On the surface of the dielectric green sheet, a conductive paste for internal electrodes is applied in a predetermined pattern by various printing methods such as screen printing or transfer methods. Then, after laminating a plurality of dielectric green sheets with internal electrode patterns formed thereon in multiple layers, a dielectric green sheet laminate is obtained by pressing in the lamination direction. At this time, on the upper and lower surfaces of the dielectric green sheet laminate in the lamination direction, the dielectric green sheet and the internal electrode pattern can be laminated so that the dielectric green sheet is positioned.

[0131] Optionally, the obtained dielectric green sheet laminate can be cut into a predetermined size by dicing or the like.

[0132] Also, the dielectric green sheet laminate can be solidified and dried to remove a plasticizer or the like if necessary, and can be barrel polished using a horizontal centrifugal barrel polishing machine or the like after solidification and drying. In barrel polishing, the dielectric green sheet laminate is put into a barrel container together with media and a polishing liquid, and by applying rotational motion, vibration, etc. to the barrel container, unnecessary parts such as burrs generated during cutting can be polished. Also, after barrel polishing, the dielectric green sheet laminate can be washed with a cleaning liquid such as water and dried.

[0133] The dielectric green sheet laminate is subjected to a debinding process and a firing process to obtain a capacitor body.

[0134] The conditions of the debinding process can be appropriately adjusted according to the main component composition of the dielectric layer and the main component composition of the internal electrode. For example, the heating rate during the debinding process may be 5 °C / hour to 300 °C / hour, the holding temperature may be 180 °C to 400 °C, and the temperature holding time may be 0.5 hour to 24 hours. The debinding atmosphere may be air or a reducing atmosphere.

[0135] The conditions of the firing process can be appropriately adjusted according to the main component composition of the dielectric layer and the main component composition of the internal electrodes. For example, the temperature during firing may be 1200°C to 1350°C, or 1220°C to 1300°C, and the time may be 0.5 hours to 8 hours, or 1 hour to 3 hours. The firing atmosphere may be a reducing atmosphere. For example, it may be an atmosphere in which a mixed gas of nitrogen gas (N2) and hydrogen gas (H2) is humidified. When the internal electrode contains nickel (Ni) or a nickel (Ni) alloy, the oxygen partial pressure in the firing atmosphere may be 1.0×10 -14 MPa to 1.0×10 -10 MPa.

[0136] After the firing process, annealing can be carried out as necessary. Annealing is a process for re-oxidizing the dielectric layer. When the firing process is carried out in a reducing atmosphere, annealing can be carried out. The conditions of the annealing process can also be appropriately adjusted according to the main component composition of the dielectric layer, etc. For example, the temperature during annealing may be 950°C to 1150°C, the time may be 0 hours to 20 hours, and the heating rate may be 50°C / hour to 500°C / hour. The annealing atmosphere may be a humidified nitrogen gas (N2) atmosphere, and the oxygen partial pressure may be 1.0×10 -9 MPa to 1.0×10 -5 MPa.

[0137] In the debinding process, the firing process, or the annealing process, in order to humidify nitrogen gas, a mixed gas, etc., for example, a wetter can be used. In this case, the water temperature may be 5°C to 75°C. The debinding process, the firing process, and the annealing process can be carried out continuously or independently.

[0138] Optionally, surface treatment such as sandblasting, laser irradiation, or barrel polishing can be performed on the third and fourth surfaces of the obtained capacitor body. By performing such surface treatment, the ends of the first internal electrode and the second internal electrode are exposed on the outermost surfaces of the third and fourth surfaces, thereby improving the electrical connection between the first external electrode and the second external electrode and the first internal electrode and the second internal electrode, and making it easier to form an alloy portion.

[0139] Next, a paste for forming a sintered metal layer can be applied to the outer surface of the obtained capacitor body and then sintered to form a sintered metal layer.

[0140] The paste for forming a sintered metal layer can contain a conductive metal and glass. Since the description of the conductive metal and glass is the same as that described above, repeated descriptions are omitted. Further, the paste for forming a sintered metal layer can optionally contain sub-components such as a binder, a solvent, a dispersant, a plasticizer, or an oxide powder. For example, ethyl cellulose, acrylic, or butyral can be used as the binder, and organic solvents such as terpineol, butyl carbitol, alcohol, methyl ethyl ketone, acetone, or toluene, or aqueous solvents can be used as the solvent.

[0141] As a method of applying the paste for forming a sintered metal layer to the outer surface of the capacitor body, a dipping method, various printing methods such as screen printing, an application method using a dispenser, or a spraying method using a spray can be used. The paste for forming a sintered metal layer is applied to at least the third and fourth surfaces of the capacitor body, and can also be applied to a part of the first surface, the second surface, the fifth surface, or the sixth surface where the band portions of the first external electrode and the second external electrode are selectively formed.

[0142] Thereafter, the capacitor body coated with the paste for forming a sintered metal layer is dried and sintered at a temperature of 700°C to 1000°C for 0.1 hour to 3 hours to form a sintered metal layer.

[0143] Alternatively, a conductive resin layer can be formed by applying a paste for forming a conductive resin layer onto the outer surface of the obtained capacitor body and then curing it.

[0144] The paste for forming a conductive resin layer can contain a resin and, optionally, a conductive metal or a non-conductive filler. Since the descriptions of the conductive metal and the resin are the same as those described above, repeated descriptions will be omitted. Further, the paste for forming a conductive resin layer can optionally contain sub-components such as a binder, a solvent, a dispersant, a plasticizer, or oxide powder. For example, ethyl cellulose, acrylic, or butyral can be used as the binder, and organic solvents such as terpineol, butyl carbitol, alcohol, methyl ethyl ketone, acetone, or toluene, or aqueous solvents can be used as the solvent.

[0145] As an example, the conductive resin layer can be formed by dipping the capacitor body 110 into the paste for forming a conductive resin layer and then curing it, or by printing the paste for forming a conductive resin layer onto the surface of the capacitor body 110 by a screen printing method or a gravure printing method, or by applying the paste for forming a conductive resin layer onto the surface of the capacitor body 110 and then curing it.

[0146] Next, a plating layer is formed outside the conductive resin layer.

[0147] As an example, the plating layer can be formed by a plating method and can also be formed by sputtering or electric deposition.

[0148] Hereinafter, specific embodiments of the invention will be presented. However, the embodiments described below are merely for specifically exemplifying or explaining the invention, and the scope of the invention should not be limited thereby.

Embodiment

[0149] Example 1 A slurry for a dielectric containing BaTiO3 is produced, and the dielectric slurry is coated using an on-roll coater of a head discharge method to produce a dielectric green sheet.

[0150] Next, Ni and Zr are weighed and mixed to produce a conductive paste for an internal electrode so that the content of Zr with respect to the entire internal electrode becomes 0.001 mol%.

[0151] The conductive paste is printed on the surface of the dielectric green sheet, and a dielectric green sheet (width × length × height = 3.2 mm × 2.5 mm × 2.5 mm) having a conductive paste layer formed thereon is laminated and pressed to produce a dielectric green sheet laminate.

[0152] The dielectric green sheet laminate is subjected to a plasticizing process in a nitrogen atmosphere at 400°C or lower, and then fired under conditions of a firing temperature of 1300°C or lower and a hydrogen concentration of 1.0% H2 or lower to produce a multilayer capacitor according to Example 1.

[0153] Examples 2 to 3 and Comparative Examples 1 to 3 Multilayer capacitors of Examples 2 to 3 and Comparative Examples 1 to 3 are produced in the same manner as in Example 1, except that the content of Zr with respect to the entire internal electrode is adjusted as shown in Table 1 below.

[0154] (Evaluation Example) Evaluation Example 1: Evaluation of electrode connectivity The electrode connectivity of the multilayer capacitors produced in Examples 1 to 3 and Comparative Examples 1 to 3 is evaluated.

[0155] First, prepare four laminated capacitors each, place them in an epoxy mixture and cure them. After that, polish the sides of the capacitor body 110 in the W-axis direction and the T-axis direction to the 1 / 2 point in the L-axis direction, maintain them in a vacuum atmosphere chamber after fixation, and prepare a cross-sectional sample cut from the center of the capacitor body 110 in the L-axis direction in the W-axis direction and the T-axis direction. Next, observe the cross-sectional sample with a transmission electron microscope (TEM) (observe at a magnification of 200 times) to prepare a TEM image.

[0156] Next, select an arbitrary internal electrode, draw a virtual line in the L-axis direction, and then measure the ratio of the unbroken internal electrode length to the total length of the internal electrode.

[0157] Taking the ratio of the length measured in Comparative Example 1 as Reference Value 1, describe the relative values of other Examples and Comparative Examples.

[0158] Evaluation Example 2: Evaluation of electrical characteristics (BDV, capacitance) and reliability (MTTF) Evaluate the breakdown voltage (BDV), capacitance, and MTTF of the laminated capacitors manufactured in Examples 1 to 3 and Comparative Examples 1 to 3, and show the results in Table 1.

[0159] To measure the BDV, prepare 50 laminated capacitors each, apply a voltage in a sweep manner from 0V to 1.00000V up to 1100V using a Keithley measuring instrument model 2410, and measure the voltage value at the moment when the current value reaches 20mA as the breakdown voltage value. The breakdown voltage is measured in a silicon oil bath. Taking the BDV of Comparative Example 1 as Reference Value 1, describe the relative values of other Examples and Comparative Examples.

[0160] The capacitance is measured using an LCR meter under the conditions of 1kHz and AC 0.5V. Taking the capacitance of Comparative Example 1 as Reference Value 1, describe the relative values of other Examples and Comparative Examples in Table 2.

[0161] The MTTF (Mean Time To Failure) value is measured by performing a high-temperature load test on 400 samples for each of the above-described examples and comparative examples under the conditions of 125°C and 8V. At this time, the time when the insulation resistance becomes 10 kΩ or less is defined as the failure time, and the relative values of the other examples and comparative examples are described in Table 1 with the MTTF value of Comparative Example 1 as the reference value 1.

[0162]

Table 1

[0163] Referring to Table 1, in the case of Examples 1 to 3, as the Zr content in the internal electrode increases from 0.001 mol% to 1 mol%, the electrode connectivity increases due to the internal electrode shrinkage delay effect, and it can be confirmed that the capacitance increases accordingly.

[0164] However, in the case of Comparative Example 2, it can be confirmed that excessive Zr diffused into the dielectric layer, causing side effects in the dielectric and resulting in a decrease in electrode connectivity and capacitance compared to Comparative Example 1.

[0165] Also, in the case of Examples 1 to 3, it can be confirmed that the BDV (Break Down Voltage) and MTTF (reliability) increased due to the increased interface reliability between the dielectric layer and the internal electrode.

[0166] However, in the case of Comparative Example 3 containing excessive Zr, it can be confirmed that the BDV and MTTF decreased compared to Comparative Example 1.

[0167] Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made and implemented within the scope of the claims, the detailed description of the invention, and the accompanying drawings, and it is natural that these also belong to the scope of the present invention.

Explanation of Reference Numerals

[0168] 100: Multilayer capacitor 110: Capacitor body 111: Dielectric layer 112, 113: Cover region 121: First internal electrode 122: Second internal electrode 131: First external electrode 132: Second external electrode

Claims

1. A capacitor body including a dielectric layer and internal electrodes, and an external electrode disposed outside the capacitor body, wherein the internal electrodes contain zirconium (Zr), and an average content of the zirconium (Zr) with respect to the entire internal electrodes is 0.0005 mol% or more and less than 5.0 mol%, wherein the dielectric layer includes a plurality of dielectric crystallites, and at least one or more of the plurality of dielectric crystallites have a core-shell structure, and the core, the shell, or all of them contain zirconium (Zr), a multilayer capacitor.

2. The multilayer capacitor according to claim 1, wherein the internal electrodes contain a conductive metal and the zirconium (Zr).

3. The dielectric crystallites contain a main component and a subcomponent, The main component is Ba ｍ TiO ３ (0.995 ≤ m ≤ 1.010), (Ba １－ｘ Ca ｘ ) ｍ (Ti １－ｙ Zr ｙ )O ３ (0.995 ≤ m ≤ 1.010, 0 ≤ x ≤ 0.10, 0 < y ≤ 0.20), Ba ｍ (Ti １－ｘ Zr ｘ )O ３ (0.995 ≤ m ≤ 1.010, x ≤ 0.10), (Ba １－ｘ Ca ｘ ) ｍ (Ti １－ｙ Sn ｙ )O ３ (0.995 ≤ m ≤ 1.010, 0 ≤ x ≤ 0.10, 0 < y ≤ 0.20), or a combination thereof, the multilayer capacitor according to claim 1.

4. The subcomponent contains zirconium (Zr), manganese (Mn), chromium (Cr), silicon (Si), aluminum (Al), magnesium (Mg), tin (Sn), antimony (Sb), hafnium (Hf), germanium (Ge), gallium (Ga), indium (In), lanthanum (La), yttrium (Y), actinium (Ac), 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), lutetium (Lu), or a combination thereof. The multilayer capacitor according to claim 3.

5. The multilayer capacitor according to claim 1, wherein the average content of the zirconium (Zr) with respect to the entire internal electrodes is 0.001 mol% to 1.0 mol%.

6. The multilayer capacitor according to claim 1, wherein an average content of the zirconium (Zr) contained in the shell with respect to the entire shell is larger than an average content of the zirconium (Zr) contained in the core with respect to the entire core.

7. The multilayer capacitor according to claim 1, wherein the average content of the zirconium (Zr) contained in the shell with respect to the entire shell is 0.001 mol% to 10.0 mol%.

8. The multilayer capacitor according to claim 1, wherein the average content of the zirconium (Zr) contained in the core with respect to the entire core is 0 mol% to 2.0 mol%.

9. The laminated capacitor according to claim 1, wherein an average thickness of the dielectric layer is from 0.1 μm to 5 μm.

10. The laminated capacitor according to claim 1, wherein an average thickness of the internal electrode is from 0.1 μm to 2 μm.

11. A capacitor body including a dielectric layer and an internal electrode, and an external electrode disposed outside the capacitor body, wherein the internal electrode includes a conductive metal and zirconium (Zr), wherein an average content of the zirconium (Zr) with respect to the entire internal electrode is 0.0005 mol% or more and less than 5.0 mol%, wherein the dielectric layer includes a plurality of dielectric crystallites, wherein at least one or more of the plurality of dielectric crystallites have a core-shell structure, the laminated capacitor, wherein the core, the shell, or all of these contain zirconium (Zr).

12. The dielectric crystallite includes a main component and a sub-component. The main component is Ba ｍ TiO ３ (0.995 ≤ m ≤ 1.010), (Ba １－ｘ Ca ｘ ) ｍ (Ti １－ｙ Zr ｙ )O ３ (0.995 ≤ m ≤ 1.010, 0 ≤ x ≤ 0.10, 0 < y ≤ 0.20), Ba ｍ (Ti １－ｘ Zr ｘ )O ３ (0.995 ≤ m ≤ 1.010, x ≤ 0.10), (Ba １－ｘ Ca ｘ ) ｍ (Ti １－ｙ Sn ｙ )O ３ (0.995 ≤ m ≤ 1.010, 0 ≤ x ≤ 0.10, 0 < y ≤ 0.20), or a combination thereof, the multilayer capacitor according to claim 11.

13. The laminated capacitor according to claim 12, wherein the sub-component includes zirconium (Zr), manganese (Mn), chromium (Cr), silicon (Si), aluminum (Al), magnesium (Mg), tin (Sn), antimony (Sb), hafnium (Hf), germanium (Ge), gallium (Ga), indium (In), lanthanum (La), yttrium (Y), actinium (Ac), 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), lutetium (Lu), or a combination thereof.

14. The laminated capacitor according to claim 11, wherein an average content of the zirconium (Zr) with respect to the entire internal electrode is 0.001 mol% to 1.0 mol%.

15. The laminated capacitor according to claim 11, wherein an average content of the zirconium (Zr) contained in the shell with respect to the entire shell is greater than an average content of the zirconium (Zr) contained in the core with respect to the entire core.

16. The laminated capacitor according to claim 11, wherein an average content of the zirconium (Zr) contained in the shell with respect to the entire shell is 0.001 mol% to 10.0 mol%.

17. The laminated capacitor according to claim 11, wherein an average content of zirconium (Zr) contained in the core with respect to the entire core is 0 mol% to 2.0 mol%.

18. The laminated capacitor according to claim 11, wherein an average thickness of the dielectric layer is 0.1 μm to 5 μm.

19. The laminated capacitor according to claim 11, wherein an average thickness of the internal electrode is 0.1 μm to 2 μm.

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