Multilayer ceramic capacitor

Abstract

To provide a multilayer ceramic capacitor with improved capacity, reliability, and temperature characteristics.SOLUTION: A multilayer ceramic capacitor according to the present disclosure includes a capacitor body including a dielectric layer and an internal electrode, and an external electrode disposed on the outside of the capacitor body. The multilayer ceramic capacitor includes Ti and Ge, and the Ge content in the multilayer ceramic capacitor is 0.01 mole to 20 moles per 100 moles of Ti.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] Recently, as electronic devices have rapidly become more multifunctional and smaller, electronic components have also rapidly become smaller and their performance has improved. In addition, there has been a significant increase in the demand for high reliability in electronic devices used in automobiles, network equipment, etc., and in industrial applications.

[0003] To meet these market needs, the technological development race for passive components such as inductors, capacitors, and resistors is accelerating. In particular, the use and volume of multilayer ceramic capacitors (MLCCs) as passive components is continuously increasing, and various product development efforts are being made to stay ahead of the market.

[0004] Multilayer ceramic capacitors are capacitors manufactured by stacking dielectric layers and internal electrodes in multiple layers, and are used in various electronic devices such as mobile phones, notebook computers, and LCD TVs.

[0005] Recently, technological advances have led to demands for miniaturization and higher capacitance in multilayer ceramic capacitors, which requires a reduction in the thickness of the internal electrodes and dielectric layers. As the thickness of the dielectric layers decreases, the electric field strength applied to each layer becomes relatively stronger, which can lead to a decrease in the reliability of the capacitor and a decrease in capacitance due to deterioration of electrode connectivity. Summary of the Invention [Problem to be solved by the invention]

[0006] One aspect of the embodiment provides a multilayer ceramic capacitor with improved capacitance, reliability, and temperature characteristics.

[0007] However, the problems to be solved by the embodiments are not limited to the above problems, and can be variously expanded within the scope of the technical ideas included in the embodiments. [Means for solving the problem]

[0008] According to one embodiment, a multilayer ceramic capacitor includes a capacitor body including a dielectric layer and an internal electrode, and an external electrode disposed on the outside of the capacitor body. The multilayer ceramic capacitor includes Ti and Ge, and the Ge content in the multilayer ceramic capacitor is 0.01 mole to 20 moles per 100 moles of Ti.

[0009] The dielectric layer contains the Ti and the Ge, the internal electrode contains Ni and the Ge, and when the average content (mol) of Ge per 100 mol of Ni in the internal electrode is X and the average content (mol) of Ge per 100 mol of Ti in the dielectric layer is Y, the relationship between X and Y can satisfy the following formula 1. [Formula 1] X / Y≧1

[0010] The X may be 0.1 to 15 moles.

[0011] The Y may be 0.05 to 10 moles.

[0012] The dielectric layer includes a plurality of dielectric crystal grains and a grain boundary between at least two of the dielectric crystal grains, and the dielectric crystal grains include a main component and a subcomponent, 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 may include combinations thereof.

[0013] The sub-components may include Ge, Dy, V, Mn, Cr, Si, Al, Mg, Sn, Sb, Ga, In, Ba, La, Y, Ac, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb, Lu, Hf, or combinations thereof.

[0014] The average thickness of the internal electrode may be 0.05 μm to 2 μm.

[0015] The average thickness of the dielectric layer may be 0.05 μm to 10 μm.

[0016] A multilayer ceramic 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 multilayer ceramic capacitor includes Ti and Ge. In the multilayer ceramic capacitor, the content of Ge with respect to 100 mol of Ti is 0.01 mol to 20 mol. The dielectric layer includes a plurality of dielectric crystal grains and a grain boundary between at least two or more of the dielectric crystal grains. The grain boundary includes the Ge, Ge oxide, or combinations thereof.

[0017] The dielectric crystal grains include a main component and a sub-component. The main component is Ba m TiO3(0.995 ≤ m ≤ 1.010), (Ba 1-x Ca x ) m (Ti1-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 may include combinations thereof.

[0018] The sub-component may include Ge, Zr, Mn, Cr, Si, Al, Mg, Sn, Sb, Hf, Ga, In, La, Y, Ac, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, or combinations thereof.

[0019] The dielectric crystal grains may further include the Ge, Ge oxide, or combinations thereof.

[0020] The internal electrode may include a conductive metal and the Ge.

[0021] The internal electrode may include an alloy of a conductive metal and Ge.

[0022] The external electrode includes a sintered metal layer that contacts the capacitor body, and the sintered metal layer may include a conductive metal and the Ge.

[0023] The average thickness of the internal electrode may be from 0.05 μm to 2 μm.

[0024] The average thickness of the dielectric layer may be from 0.05 μm to 10 μm.

Advantages of the Invention

[0025] The multilayer ceramic capacitor according to the embodiment has the advantages of improved capacitance, reliability, and temperature characteristics.

[0026] However, the various beneficial advantages and effects of the present invention are not limited to the above, and will be more easily understood in the course of describing specific embodiments of the present invention. [Brief explanation of the drawings]

[0027] [Figure 1] FIG. 1 is a perspective view showing a multilayer ceramic capacitor according to an embodiment. [Figure 2] FIG. 2 is a cross-sectional view of the multilayer ceramic capacitor taken along line II' in FIG. [Figure 3] FIG. 3 is an exploded perspective view showing the laminated structure of the internal electrodes in the capacitor body of FIG. DETAILED DESCRIPTION OF THE INVENTION

[0028] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily understand the present invention. In the drawings, parts unnecessary for explanation are omitted in order to clearly explain the present invention, and the same reference numerals are used throughout the specification to refer to the same or similar components. Furthermore, the accompanying drawings are only intended to facilitate understanding of the embodiments disclosed in this specification, and the accompanying drawings should not be construed as limiting the technical ideas disclosed in this specification, and should be understood to include any modifications, equivalents, or alternatives within the idea and technical scope of the present invention.

[0029] Terms including ordinal numbers such as first, second, etc. may be used to describe various components, but the components are not limited by the terms. The terms are used only to distinguish one component from another.

[0030] When a component is referred to as being "coupled" or "connected" to another component, it should be understood that the component may be directly coupled to, connected to, or opposite the other component, but that there may be other components in between.

[0031] In contrast, when a component is said to be "directly coupled" or "directly connected" to another component, it should be understood that there are no other components in between.

[0032] Throughout the specification, the use of terms such as "comprises" or "having" is intended to specify the presence of any feature, number, step, operation, component, part, or combination thereof described in the specification, but should be understood to not preclude the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof. Thus, when a part is described as "comprising" certain elements, this does not mean that it can further include other elements, but does not exclude other elements, unless specifically stated to the contrary.

[0033] Hereinafter, various embodiments and modifications will be described in detail with reference to the drawings.

[0034] FIG. 1 is a perspective view showing a multilayer ceramic capacitor 100 according to one embodiment, FIG. 2 is a cross-sectional view of the multilayer ceramic capacitor 100 taken along line II' in FIG. 1, and FIG. 3 is an exploded perspective view showing the laminated structure of internal electrodes 121 and 122 in the capacitor body 110 of FIG. 1.

[0035] To clarify the present embodiment, the L-axis, W-axis, and T-axis shown in the drawings represent the length, width, and thickness directions of the capacitor body 110, respectively. Here, the thickness direction (T-axis direction) may be perpendicular to the wide surface (main surface) of the sheet-shaped component, and may be the same concept as the stacking direction of the dielectric layers 111. The length direction (L-axis direction) may be substantially perpendicular to the thickness direction (T-axis direction) in a direction extending parallel to the wide surface (main surface) of the sheet-shaped component, and 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 substantially perpendicular to the thickness direction (T-axis direction) and the length direction (L-axis direction) in a direction extending parallel to the wide surface (main surface) of the sheet-shaped component, and the length of the length direction (L-axis direction) of the sheet-shaped component may be longer than the length of the width direction (W-axis direction).

[0036] 1 to 3, a multilayer ceramic capacitor 100 according to one embodiment may include a capacitor body 110, and a first external electrode 131 and a second external electrode 132 disposed at opposite ends of the capacitor body 110 in a longitudinal direction (L-axis direction).

[0037] A multilayer ceramic capacitor 100 according to one embodiment includes a capacitor body 110 including a dielectric layer 111 and internal electrodes 121 and 122, and external electrodes 131 and 132 disposed on the outside of the capacitor body 110. The multilayer ceramic capacitor 100 includes Ti and Ge, and the content of Ge per 100 moles of Ti in the multilayer ceramic capacitor 100 is 0.01 mole to 20 moles.

[0038] The present disclosure has the advantage that by optimizing the Ge content in the multilayer ceramic capacitor 100, the capacitance, reliability, and temperature characteristics of the multilayer ceramic capacitor can all be improved.

[0039] In the multilayer ceramic capacitor 100, if the content of Ge relative to 100 moles of Ti is less than 0.01 moles, the temperature characteristics of the capacitor cannot be sufficiently improved, and if it exceeds 20 moles, it may be difficult to sufficiently improve the reliability of the capacitor.

[0040] In the multilayer ceramic capacitor 100 according to one embodiment, the dielectric layer 111 includes a plurality of dielectric crystal grains and a grain boundary between at least two of the dielectric crystal grains, and the grain boundary includes the Ge, a Ge oxide, or a combination thereof.

[0041] For example, the dielectric crystal grains may include a main component and a subcomponent, and the dielectric crystal grains may further include Ge, Ge oxide, or a combination thereof. The main component and the subcomponent contained in the dielectric crystal grains will be described later.

[0042] For example, the internal electrodes 121 and 122 may include a conductive metal and Ge. For a specific example, the internal electrodes 121 and 122 may include an alloy of a conductive metal and Ge.

[0043] For example, the external electrode may include a sintered metal layer in contact with the capacitor body 110, and the sintered metal layer may include a conductive metal and the Ge.

[0044] Ge (Germanium) is an element that has a stronger tendency to oxidize than Ni, which is the main material of the internal electrodes 121 and 122 .

[0045] When such Ge is added to a conductive paste for forming an internal electrode during the manufacture of a multilayer ceramic capacitor and fired together with Ni in a reducing atmosphere, some of the Ge may be evenly present in the form of a Ni-Ge alloy within the internal electrodes 121 and 122.

[0046] The Ni-Ge alloy reduces the grain boundary energy and surface tension of Ni, thereby improving the smoothness and connectivity of the internal electrodes 121 and 122. When the smoothness of the internal electrodes 121 and 122 is improved, the strength of the electric field applied to each dielectric layer 111 can be dispersed even if the thickness of the dielectric layer 111 is reduced.

[0047] Furthermore, alloying Ge, which is a semimetal, with Ni improves the insulation properties of the interface between the dielectric layer 111 and the internal electrodes 121 and 122, thereby improving reliability. In addition, Ni slows down the sintering rate during the alloying process with Ge, which further improves electrode connectivity and allows for the realization of a capacitor with higher capacitance.

[0048] The remaining Ge may diffuse into the dielectric layer 111 in the form of Ge or Ge oxide (GeO2), and at this time, the Ge or Ge oxide may diffuse evenly along the grain boundaries in the dielectric layer 111. A portion of the Ge or Ge oxide may also diffuse into the interior of the dielectric grains.

[0049] In this case, since the Ge oxide has a lower melting point than BaTiO3, which is the main component of the dielectric crystal grains, the Ge oxide may become liquid during the firing process of the capacitor. The liquid Ge oxide can promote grain growth of the dielectric crystal grains, thereby increasing the dielectric constant of the capacitor.

[0050] Furthermore, the dielectric crystal grains may have a core-shell structure, and in this case, the liquid-phase Ge oxide can increase the shell fraction in the dielectric crystal grains, thereby improving the capacitance change rate characteristics of the capacitor with respect to temperature.

[0051] The method for measuring the Ge content relative to Ti in the multilayer ceramic capacitor 100 is as follows.

[0052] First, a sample of the multilayer ceramic capacitor 100 was prepared. 0.1 g of the sample was weighed and placed in a pressure bottle. 6 ml of hydrochloric acid and 2 ml of nitric acid were added to prepare a mixture. The mixture was then heat-treated at approximately 180°C for approximately one hour and subjected to additional sonication to prepare a dissolved sample. The dissolved sample was filtered through a 0.45 μm filter and analyzed for the Ti and Ge contents (wt%) in the sample using an inductively coupled plasma-optical emission spectrometry (ICP-OES). The wt% of each element was then converted to mol%, and the Ge mol% was then converted per 100 moles of Ti to determine the Ge content in the multilayer ceramic capacitor 100.

[0053] [Capacitor body] The capacitor body 110 may be, for example, substantially hexahedral in shape.

[0054] In this embodiment, for ease of explanation, the two 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, the two 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 the two surfaces that are connected to the first surface and the second surface and are 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.

[0055] As an example, the first surface, which is the bottom surface, may be the surface facing the mounting direction. Furthermore, the first to sixth surfaces may be flat, but this embodiment is not limited to this. For example, the first to sixth surfaces may be curved surfaces with convex central portions, and the corners that are the boundaries between the surfaces may be rounded.

[0056] The shape and size of the capacitor body 110 and the number of laminated dielectric layers 111 are not limited to those shown in the drawings of this embodiment.

[0057] The capacitor body 110 is formed by stacking a plurality of dielectric layers 111 in the thickness direction (T-axis direction) and then firing the layers, and includes first internal electrodes 121 and second internal electrodes 122 that are alternately arranged in the thickness direction (T-axis direction) with the plurality of dielectric layers 111 sandwiched between them.

[0058] At this time, the boundaries between the adjacent dielectric layers 111 of the capacitor body 110 may be integrated to such an extent that it is difficult to identify them without using a scanning electron microscope (SEM).

[0059] The capacitor body 110 may also include an active area and cover areas 112 and 113 .

[0060] The active region is a portion that contributes to forming the capacitance of the multilayer ceramic capacitor 100. For example, the active region may be an overlapping region of the first internal electrode 121 or the second internal electrode 122 that are stacked along the thickness direction (T-axis direction).

[0061] The cover regions 112 and 113 may be margins in the thickness direction and may be located on the first and second sides of the active region in the thickness direction (T-axis direction). These cover regions 112 and 113 may be a single dielectric layer 111 or two or more dielectric layers 111 stacked on the upper and lower surfaces of the active region, respectively.

[0062] The capacitor body 110 may further include side cover regions. The side cover regions may be widthwise margins located on the fifth and sixth sides of the active region in the width direction (W-axis direction). These side cover regions may be formed by applying a conductive paste layer for forming internal electrodes to only a portion of the surface of the dielectric green sheet, stacking dielectric green sheets without the conductive paste layer on both side surfaces of the surface of the dielectric green sheet, and then firing the stack.

[0063] The cover regions 112 and 113 and the side cover regions serve to prevent the first internal electrode 121 and the second internal electrode 122 from being damaged by physical or chemical stress.

[0064] [Dielectric layer] The dielectric layer 111 includes a dielectric material, and the dielectric material may include a main component and a subcomponent.

[0065] The main component is a base material of the dielectric, has a high dielectric constant, and contributes to forming the dielectric constant of the multilayer ceramic capacitor 100 .

[0066] The dielectric layer 111 includes a plurality of dielectric crystal grains and a grain boundary between at least two of the dielectric crystal grains, and the grain boundary includes the Ge, a Ge oxide, or a combination thereof.

[0067] For example, the dielectric grains may include a major component and a minor component, and the dielectric grains may further include Ge, Ge oxide, or a combination thereof.

[0068] For example, the main component may be a barium titanate-based compound, such as Ba m TiO3(0.995≦m≦1.010), (Ba 1-x Ca x ) m (Ti 1-y Zry )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 it may be a dielectric material containing a combination of these.

[0069]

[0070]

[0071]

[0072] 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 of these. As an example, the sub-component may include germanium (Ge), dysprosium (Dy), vanadium (V), manganese (Mn), chromium (Cr), silicon (Si), aluminum (Al), magnesium (Mg), tin (Sn), antimony (Sb), gallium (Ga), indium (In), barium (Ba), lanthanum (La), yttrium (Y), actinium (Ac), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), or a combination of these. The dielectric may further contain a ceramic additive, an organic solvent, a binder, a dispersant, or a combination of these.For example, at least one of the plurality of dielectric crystal grains may have a core-shell structure.

[0073] A dielectric crystal grain having a core-shell structure includes a dielectric core and a shell surrounding at least a portion of the core within a single dielectric crystal grain. For example, the Ge or Ge oxide may be mainly contained in the grain boundaries, but a portion of the Ge or Ge oxide may be diffused into the shell within the dielectric crystal grain.

[0074] The molar ratio of the minor component to the major component differs between the core and shell, and for example, the molar ratio of the minor component to the major component may change suddenly at the boundary between the core and shell. This makes it easy to distinguish the boundary between the core and shell, and can be confirmed using transmission electron microscope-energy dispersive X-ray analysis (TEM-EDX).

[0075] For example, the core may contain minor components, or only trace amounts, if any. Therefore, the core may be composed of only a pure main component without impurities, and a pure main component may generally have a higher dielectric constant than a main component doped with an impurity element. Thus, the core may play a role in maintaining the dielectric constant.

[0076] The shell contains more minor components than the core. The minor components doped into the B site of the main component (perovskite ABO3 structure) in the shell have the effect of increasing the band gap energy, which allows other rare earth elements and doping elements to diffuse into the dielectric crystal grains. This allows the shell to act as a barrier that prevents other rare earth elements and doping elements from diffusing into the dielectric crystal grains. The shell also serves to suppress the growth of dielectric crystal grains, contributing to the miniaturization of the dielectric crystal grains. In addition, the minor components doped into the A site of the main component in the shell can improve reliability and dielectric constant.

[0077] As an example, the average thickness of the dielectric layer 111 may be 0.05 μm or more, 0.1 μm or more, or 0.2 μm or more, and may be 10 μm or less, 5 μm or less, 2.5 μm or less, or 2.0 μm or less.

[0078] The average thickness of the dielectric layer 111 can be measured by the following method.

[0079] First, a cross-sectional sample is observed with a scanning electron microscope (SEM) to prepare a scanning electron microscope image.

[0080] It may also be the arithmetic mean value of the thickness of the dielectric layer 111 at 10 points spaced apart at a predetermined interval from the center point of the dielectric layer 111 in the length direction (L-axis direction) or width direction (W-axis direction) in a scanning electron microscope (SEM) image of the cross-sectional sample.

[0081] The spacing between the 10 dots can be adjusted according to the scale of the scanning electron microscope (SEM) image, and may be, for example, 1 μm to 100 μm, 1 μm to 50 μm, or 1 μm to 10 μm.

[0082] In this case, all 10 points must be located within the dielectric layer 111, and if none of the 10 points are located within the dielectric layer 111, the position of the reference point can be changed or the spacing between the 10 points can be adjusted.

[0083] [Internal electrode] The internal electrodes may include a first internal electrode 121 and a second internal electrode 122. The first internal electrode 121 and the second internal electrode 122 have different polarities and are alternately arranged to face each other along the T-axis direction with the dielectric layer 111 interposed therebetween. One end of each electrode may be exposed through a third and fourth surface of the capacitor body 110.

[0084] The first internal electrode 121 and the second internal electrode 122 can be electrically insulated from each other by the dielectric layer 111 disposed therebetween.

[0085] The ends of the first internal electrode 121 and the second internal electrode 122, which are alternately exposed through the third and fourth surfaces of the capacitor body 110, can be connected to and electrically coupled with the first external electrode 131 and the second external electrode 132, respectively.

[0086] In an embodiment, the first internal electrode 121 and the second internal electrode 122 may include a conductive metal and Ge, and as a specific example, may include an alloy of a conductive metal and Ge.

[0087] For example, the conductive metal may further include a metal such as Ni, Cu, Ag, Pd, or Au, or an alloy thereof, such as an Ag-Pd alloy. For example, when the conductive metal is Ni, the first internal electrode 121 and the second internal electrode 122 may include Ni and Ge, for example, a Ni-Ge alloy.

[0088] Furthermore, the first internal electrode 121 and the second internal electrode 122 may contain dielectric particles of the same composition as the ceramic material contained in the dielectric layer 111 .

[0089] The first internal electrode 121 and the second internal electrode 122 can be formed using a conductive paste containing a conductive metal and Ge. The conductive paste can be printed by screen printing, gravure printing, or the like.

[0090] In one embodiment, the dielectric layer 111 may include Ti and Ge, and the internal electrodes 121 and 122 may include Ni and Ge. When the average content (mol) of Ge per 100 mol of Ni in the internal electrodes 121 and 122 is X, and the average content (mol) of Ge per 100 mol of Ti in the dielectric layer 111 is Y, the relationship between X and Y may satisfy the following formula 1: [Formula 1] X / Y≧1

[0091] For example, in the above formula 1, X / Y may be greater than 1, for example, 1.4 or greater, or 1.6 or greater.

[0092] In the above formula 1, if the X / Y value is less than 1, there will be an excess amount of Ge in the dielectric layer compared to the internal electrodes, which may cause problems such as a decrease in dielectric constant.

[0093] For example, X may be 0.1 mol to 15 mol. For example, X may be 0.25 mol or more, or 0.5 mol or more, or may be 10 mol or less, 5 mol or less, or 3 mol or less.

[0094] For example, Y may be 0.05 mol to 10 mol. For example, Y may be 0.1 mol or more, 0.2 mol or more, or 0.3 mol or more, and may be 5 mol or less, 2.5 mol or less, 2 mol or less, or 1.4 mol or less.

[0095] When the above numerical ranges are satisfied, a multilayer ceramic capacitor with improved capacitance, reliability, and temperature characteristics can be realized.

[0096] The X and Y values ​​are determined as follows.

[0097] First, the multilayer ceramic capacitor 100 is placed in an epoxy mixture and hardened, and then the sides of the capacitor body 110 in the L-axis direction and the T-axis direction are polished to the halfway point in the W-axis direction, fixed, and then maintained in a vacuum chamber to prepare cross-sectional samples cut in the L-axis direction and the T-axis direction at the center of the W-axis direction of the capacitor body 110.

[0098] Thereafter, a TEM image of the cross-sectional sample is prepared, and then five or more arbitrary dielectric layers 111 and arbitrary internal electrodes 121 and 122 are selected from the image.

[0099] Then, five equally spaced points corresponding to the center of the selected dielectric layer 111 are selected, and the contents (moles) of Ti and Ge are measured at the selected points through a TEM (Transmission Electron Microscope)-EDS (Energy Disperse X-Ray Spectrometer) quantitative analysis, and the arithmetic mean value of the measured values ​​is calculated to obtain the X value.

[0100] In addition, five equally spaced points corresponding to the center of the selected internal electrodes 121 and 122 are selected, and the Ni and Ge contents (moles) are measured at the selected points through TEM-EDS quantitative analysis, and the arithmetic mean value of the measured values ​​is calculated to obtain the Y value.

[0101] For example, the center of the dielectric layer 111 may refer to a midpoint between a point on one surface of one of the dielectric layers 111 and a point on the other surface of the dielectric layer 111 that is closest to the point in a cross section cut in the L-axis and T-axis directions at the center of the W-axis direction of the capacitor body 110. Also, it may refer not only to the midpoint but also to a region within ±30% in the T-axis direction from the midpoint.

[0102] For example, the center of the internal electrodes 121 and 122 may refer to a midpoint between a point on one surface of one of the internal electrodes 121 and 122 and a point on the other surface of the internal electrodes 121 and 122 that is closest to the point in a cross section cut in the L-axis and T-axis directions at the center of the W-axis direction of the capacitor body 110. Also, it may refer not only to the midpoint but also to a region within ±30% in the T-axis direction from the midpoint.

[0103] For example, the average thickness of the first internal electrode 121 and the second internal electrode 122 may be 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, or 0.25 μm or more, or 2 μm or less, 1 μm or less, 0.5 μm or less, 0.4 μm or less, or 0.3 μm or less.

[0104] The average thickness of the first internal electrode 121 or the second internal electrode 122 can be measured by the following method.

[0105] In the scanning electron microscope (SEM) image of the cross-sectional sample, the center point of the length direction (L-axis direction) or width direction (W-axis direction) of the first internal electrode 121 or the second internal electrode 122 is set as a reference point, and the arithmetic mean value of the thickness of the first internal electrode 121 or the second internal electrode 122 at 10 points spaced apart at predetermined intervals from the reference point can be calculated to determine the average thickness of the internal electrodes 121, 122.

[0106] The spacing between the 10 dots can be adjusted according to the scale of the scanning electron microscope (SEM) image, and may be, for example, 1 μm to 100 μm, 1 μm to 50 μm, or 1 μm to 10 μm.

[0107] In this case, all 10 points must be located within the first internal electrode 121 or the second internal electrode 122, and if none of the 10 points are located within the first internal electrode 121 or the second internal electrode 122, the position of the reference point can be changed or the spacing between the 10 points can be adjusted.

[0108] [External electrode] The first external electrode 131 and the second external electrode 132 may be supplied with voltages of different polarities and may be electrically connected to the exposed portions of the first internal electrode 121 and the second internal electrode 122, respectively.

[0109] 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 opposing first internal electrode 121 and second internal electrode 122. At this time, the capacitance of the multilayer ceramic capacitor 100 is proportional to the overlap 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.

[0110] The first external electrode 131 and the second external electrode 132 may each include first and second connection portions arranged on the third and fourth surfaces of the capacitor body 110, respectively, and connecting to the first internal electrode 121 and the second internal electrode 122, and first and second band portions arranged at the corners where the third and fourth surfaces of the capacitor body 110 meet the first and second surfaces or the fifth and sixth surfaces.

[0111] The first and second band portions may extend from the first and second connection portions to parts of the first and second surfaces or the fifth and sixth surfaces of the capacitor body 110. The first and second band portions may serve to improve the bonding strength between the first external electrode 131 and the second external electrode 132.

[0112] For 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 arranged to cover the sintered metal layer, and a plating layer arranged to cover the conductive resin layer.

[0113] The sintered metal layer may include a conductive metal and Ge, and as an example, the sintered metal layer may include an alloy of a conductive metal and Ge.

[0114] The sintered metal layer may contain, as the conductive metal, 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. For example, copper (Cu) may contain a copper (Cu) alloy. For example, when the conductive metal is Cu, the sintered metal layer may contain Cu and Ge, for example, a Cu-Ge alloy. Furthermore, when the conductive metal includes copper, metals other than copper may be contained in an amount of 5 moles or less per 100 moles of copper.

[0115] For example, the sintered metal layer may further include glass. In this case, the sintered metal layer may include a glass composition containing a mixture of oxides, such as 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 may be selected from the group consisting of zinc (Zn), titanium (Ti), copper (Cu), vanadium (V), manganese (Mn), iron (Fe), and nickel (Ni). The alkali metal may be selected from the group consisting of lithium (Li), sodium (Na), and potassium (K). The alkaline earth metal may be selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba).

[0116] Alternatively, the conductive resin layer may be formed on the sintered metal layer, for example, to completely cover the sintered metal layer. Meanwhile, the first external electrode 131 and the second external electrode 132 may not include a sintered metal layer, in which case the conductive resin layer may be in direct contact with the capacitor body 110.

[0117] The conductive resin layer may extend on the first and second surfaces or the fifth and sixth surfaces of the capacitor body 110, and the length of the region (i.e., band portion) where the conductive resin layer extends 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., band portion) where the sintered metal layer extends on the first and second surfaces or the fifth and sixth surfaces of the capacitor body 110. In other words, the conductive resin layer may be formed on the sintered metal layer to completely cover the sintered metal layer.

[0118] The conductive resin layer includes a resin and a conductive metal.

[0119] The resin contained in the conductive resin layer is not particularly limited as long as it has bonding properties and impact absorbency and can be mixed with the conductive metal powder to form a paste, and may include, for example, a phenolic resin, an acrylic resin, a silicone resin, an epoxy resin, or a polyimide resin.

[0120] The conductive metal contained in the conductive resin layer serves to electrically connect the first internal electrode 121 and the second internal electrode 122 or the sintered metal layer.

[0121] The conductive metal contained in the conductive resin layer may have a spherical shape, a flake shape, or a combination thereof. That is, the conductive metal may be composed of only flake shapes, only spherical shapes, or a mixture of flake shapes and spherical shapes.

[0122] Here, the spherical shape may include a shape that is not a perfect sphere, for example, a shape in which the 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 shape, and is not particularly limited, but may, for example, have a ratio of the major axis to the minor axis (major axis / minor axis) of 1.95 or more.

[0123] The first external electrode 131 and the second external electrode 132 may further include a plating layer disposed on the outer side of the conductive resin layer.

[0124] The plating layer may include nickel (Ni), copper (Cu), tin (Sn), palladium (Pd), platinum (Pt), gold (Au), silver (Ag), tungsten (W), titanium (Ti), lead (Pb), etc., alone or in alloys thereof. For example, the plating layer may be a nickel (Ni) plating layer or a tin (Sn) plating layer, or may be a nickel (Ni) plating layer and a tin (Sn) plating layer stacked in sequence, or a tin (Sn) plating layer, a nickel (Ni) plating layer, and a tin (Sn) plating layer stacked in sequence. Furthermore, the plating layer may include multiple nickel (Ni) plating layers and / or multiple tin (Sn) plating layers.

[0125] The plating layer can improve the mountability of the multilayer ceramic capacitor 100 to a substrate, structural reliability, durability against the outside, heat resistance, and equivalent series resistance (ESR).

[0126] [Manufacturing method of multilayer ceramic capacitor] A method for manufacturing a multilayer ceramic capacitor according to another embodiment includes the steps of: forming a capacitor body including dielectric layers and internal electrodes; and forming external electrodes on the outside of the capacitor body.

[0127] First, the manufacturing of the capacitor body will be described.

[0128] In the manufacturing process of the capacitor body, a dielectric paste that will become a dielectric layer after firing and a conductive paste that will become an internal electrode after firing are prepared.

[0129] The dielectric paste is produced, for example, by the following method: Dielectric powders are uniformly mixed by means of wet mixing or the like, dried, and then heat-treated under predetermined conditions to obtain plastic powder, and an organic vehicle or an aqueous vehicle is added to the obtained plastic powder and kneaded to prepare the dielectric paste.

[0130] The obtained dielectric paste is formed into a sheet by a technique such as a doctor blade method to obtain a dielectric green sheet. The dielectric paste may also contain additives selected from various dispersants, plasticizers, dielectrics, subcomponent compounds, glass, etc., as needed.

[0131] The conductive paste for the internal electrodes is prepared by kneading a conductive powder made of a conductive metal or its alloy with a binder and a solvent.

[0132] For example, the conductive paste for the internal electrodes may be manufactured containing Ge. For example, the conductive paste for the internal electrodes may be manufactured containing a Ni-Ge alloy or a GeO powder.

[0133] The conductive paste for the internal electrodes may contain ceramic powder (for example, barium titanate powder) as a co-material, if necessary. The co-material has the effect of suppressing sintering of the conductive powder during the firing process.

[0134] A conductive paste for internal electrodes is applied in a predetermined pattern to the surface of a dielectric green sheet by various printing methods such as screen printing or transfer methods. Then, a plurality of dielectric green sheets on which the internal electrode patterns have been formed are stacked, and then pressed in the stacking direction to obtain a dielectric green sheet laminate. At this time, the dielectric green sheets and the internal electrode patterns can be stacked so that the dielectric green sheets are located on the upper and lower surfaces of the dielectric green sheet laminate in the stacking direction.

[0135] Optionally, the obtained dielectric green sheet laminate can be cut to a predetermined size by dicing or the like.

[0136] Furthermore, the dielectric green sheet laminate can be solidified and dried as needed to remove plasticizers and the like, and after solidification and drying, can be barrel polished using a horizontal centrifugal barrel machine or the like. In barrel polishing, the dielectric green sheet laminate is placed in a barrel container together with media and a polishing solution, and the barrel container is subjected to rotational motion, vibration, or the like, to polish away unnecessary parts such as burrs generated during cutting. Furthermore, after barrel polishing, the dielectric green sheet laminate can be washed with a cleaning liquid such as water and dried.

[0137] The dielectric green sheet laminate is subjected to binder removal and firing to obtain a capacitor body.

[0138] The conditions for the binder removal treatment can be appropriately adjusted depending on the main component composition of the dielectric layer and the main component composition of the internal electrode. For example, the temperature increase rate during the binder removal treatment may be 5°C / hour to 300°C / hour, the support temperature may be 180°C to 400°C, and the temperature maintenance time may be 0.5 hours to 24 hours. The binder removal atmosphere may be air or a reducing atmosphere.

[0139] The firing conditions can be appropriately adjusted depending on the main component composition of the dielectric layers and the main component composition of the internal electrodes. For example, the firing temperature may be 1200 to 1350°C, or 1220 to 1300°C, and the firing time may be 0.5 to 8 hours, or 1 to 3 hours. The firing atmosphere may be a reducing atmosphere, for example, an atmosphere of humidified mixed gas of nitrogen gas (N2) and hydrogen gas (H2). When the internal electrodes contain nickel (Ni) or a nickel (Ni) alloy, the oxygen partial pressure in the firing atmosphere may be 1.0 x 10 -14 MPa to 1.0×10 -10 It may be MPa.

[0140] After the firing treatment, annealing can be performed as needed. Annealing is a treatment for reoxidizing the dielectric layer, and can be performed when the firing treatment is performed in a reducing atmosphere. The conditions of the annealing treatment can also be appropriately adjusted depending on the main component composition of the dielectric layer, etc. For example, the annealing temperature may be 950°C to 1150°C, the annealing time may be 0 hours to 20 hours, and the temperature increase 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 x 10 -9 MPa to 1.0×10 -5 It may be MPa.

[0141] In order to humidify nitrogen gas or mixed gas in the binder removal treatment, firing treatment, or annealing treatment, for example, a wetter or the like can be used, and in this case, the water temperature may be 5° C. to 75° C. The binder removal treatment, firing treatment, and annealing treatment can be performed consecutively or independently.

[0142] Optionally, the third and fourth surfaces of the obtained capacitor body may be subjected to surface treatment such as sandblasting, laser irradiation, barrel polishing, etc. By performing such surface treatment, the ends of the first and second internal electrodes may be exposed on the outermost surfaces of the third and fourth surfaces, which may improve the electrical connection between the first and second external electrodes and the first and second internal electrodes, making it easier to form alloy parts.

[0143] Next, a paste for forming a sintered metal layer is applied to the outer surface of the obtained capacitor body as an external electrode, and then sintered to form a sintered metal layer.

[0144] The paste for forming the sintered metal layer may include a conductive metal and glass. The conductive metal and glass are the same as those described above, and therefore will not be described again. The paste for forming the sintered metal layer may optionally include a binder, a solvent, a dispersant, a plasticizer, an oxide powder, or other auxiliary components. For example, the binder may be ethyl cellulose, acrylic, or butyral, and the solvent may be an organic solvent such as terpineol, butyl carbitol, alcohol, methyl ethyl ketone, acetone, or toluene, or an aqueous solvent.

[0145] The method of applying the sintered metal layer forming paste to the outer surface of the capacitor body can be a dipping method, various printing methods such as screen printing, an application method using a dispenser, a spraying method using a spray, etc. The sintered metal layer paste is applied to at least the third and fourth surfaces of the capacitor body, and may also be applied selectively to parts of the first, second, fifth, or sixth surfaces on which the band portions of the first and second external electrodes are formed.

[0146] 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 to 3 hours to form a sintered metal layer.

[0147] Alternatively, a conductive resin layer forming paste may be applied to the outer surface of the obtained capacitor body and then cured to form a conductive resin layer.

[0148] The paste for forming the conductive resin layer may include a resin and, optionally, a conductive metal or a non-conductive filler. The conductive metal and resin are the same as those described above, and therefore will not be described again. The paste for forming the conductive resin layer may also include, optionally, a binder, a solvent, a dispersant, a plasticizer, an oxide powder, or other auxiliary components. For example, the binder may be ethyl cellulose, acrylic, or butyral, and the solvent may be an organic solvent or an aqueous solvent such as terpineol, butyl carbitol, alcohol, methyl ethyl ketone, acetone, or toluene.

[0149] For example, the conductive resin layer may be formed by dipping the capacitor body 110 in a paste for forming the conductive resin layer and then curing it, by printing the paste for forming the conductive resin layer on the surface of the capacitor body 110 using a screen printing method or a gravure printing method, or by applying the paste for forming the conductive resin layer on the surface of the capacitor body 110 and then curing it.

[0150] Next, a plating layer is formed on the outer surface of the conductive resin layer.

[0151] For example, the plating layer may be formed by a plating method, such as sputtering or electroplating (electrodeposition).

[0152] Specific examples of the present invention will be presented below. However, the examples described below are merely for the purpose of specifically illustrating or explaining the present invention, and should not be construed as limiting the scope of the present invention.

[0153] (Example) [Example 1] The multilayer ceramic capacitor according to Example 1 was manufactured by weighing Ge so that the Ge content in the multilayer ceramic capacitor was 0.05 mol relative to 100 mol of Ti, and adjusting the oxygen partial pressure conditions.

[0154] The Ge content in the multilayer ceramic capacitor was determined by the following method.

[0155] First, 0.1 g of the multilayer ceramic capacitor according to Example 1 was weighed into a pressure bottle, and 6 ml of hydrochloric acid and 2 ml of nitric acid were added to prepare a mixture. The mixture was then heat-treated at approximately 180°C for approximately 1 hour and further sonicated to prepare a dissolved sample. The dissolved sample was filtered through a 0.45 μm filter and analyzed for the Ti and Ge contents (wt%) using an inductively coupled plasma spectroscopy (ICP-OES). The wt% of each element was converted to mol%, and the Ge mol% was converted per 100 mol of Ti to determine the Ge content in the multilayer ceramic capacitor.

[0156] For reference, the weight percentages of Ni, Ba, Ti, and Ge elements measured using the ICP-OES analysis method for the multilayer ceramic capacitors according to Examples 2 to 4 are shown in Table 2 below. After converting the weight percentages of each element to mole percentages, the mole percentage of Ge is converted per 100 moles of Ti, which can be shown in Table 1 as "Ge content in multilayer ceramic capacitor (moles / 100 moles of Ti)."

[0157] In addition, for the multilayer ceramic capacitors of Examples 1 and 2, the average content (moles) of Ge per 100 moles of Ni in the internal electrodes and the average content (moles) of Ge per 100 moles of Ti in the dielectric layers were measured and are shown in Table 3 below.

[0158] The average Ge content in the internal electrodes and dielectric layers can be determined by the following method.

[0159] First, the multilayer ceramic capacitor is placed in an epoxy mixture and hardened. Then, the sides of the capacitor body in the L-axis direction and the T-axis direction are polished to the halfway point in the W-axis direction, and the capacitor is fixed in place. Then, the capacitor is maintained in a vacuum chamber, and cross-sectional samples are prepared by cutting the capacitor body in the L-axis direction and the T-axis direction at the center of the W-axis direction.

[0160] Then, after preparing a TEM image of the cross-sectional sample, five or more arbitrary dielectric layers and five or more arbitrary internal electrodes are selected from the image.

[0161] Then, five equally spaced points corresponding to the center of the selected dielectric layer are selected, and the Ti and Ge contents (moles) are measured at the selected points through a TEM (Transmission Electron Microscope)-EDS (Energy Disperse X-Ray Spectrometer) quantitative analysis, and the arithmetic mean value of the measured values ​​is calculated to obtain the X value.

[0162] In addition, five equally spaced points corresponding to the center of the selected internal electrode are selected, and the Ni and Ge contents (moles) are measured at the selected points through TEM-EDS quantitative analysis. The arithmetic mean value of the measured values ​​is calculated to obtain the Y value.

[0163] [Examples 2 to 9 and Comparative Examples 1 to 3] Multilayer ceramic capacitors according to Examples 2 to 9 and Comparative Examples 1 to 3 were manufactured by weighing Ge so that the Ge content in the multilayer ceramic capacitor was contained in the moles shown in Table 1 below and adjusting the oxygen partial pressure conditions.

[0164] (Evaluation example) [Evaluation example 1: Capacitance measurement] The capacitance of the multilayer ceramic capacitors manufactured in Examples 1 to 9 and Comparative Examples 1 to 3 was measured using an LCR meter under the conditions of 1 kHz and AC 0.5V.

[0165] The capacitance of Comparative Example 1 was set as a reference value of 1, and the relative values ​​of the other Examples and Comparative Examples were measured and shown in Table 1 below.

[0166] [Evaluation example 2: Measurement of MTTF (Mean Time To Failure)] The multilayer ceramic capacitors manufactured in Examples 1 to 9 and Comparative Examples 1 to 3 were subjected to a high temperature load test at 125° C. and 8 V to measure the MTTF (Mean Time To Failure) value.

[0167] At this time, the time until the insulation resistance became 10 kΩ or less was set as a fixed time, and the MTTF value of Comparative Example 1 was set as a reference value 1, and the relative values ​​of the other Examples and Comparative Examples were measured and shown in Table 1 below.

[0168] [Evaluation example 3: Evaluation of whether temperature characteristics are satisfactory] The capacitance change rate of the multilayer ceramic capacitors manufactured in Examples 1 to 9 and Comparative Examples 1 to 3 was measured while increasing the temperature by 1°C from -55°C to 85°C. Specifically, the capacitance was measured at each temperature under AC conditions of 1 kHz, 0.1 Vrms, and maintained for 1 minute, and the capacitance change rate at each temperature was calculated using Equation 2 with 25°C as the reference temperature. [Formula 2] Capacity change rate at X°C (%) = {(C[X°C]-C[25°C]) / C[25°C]} x 100 *C[X℃] = capacitance measured at X℃

[0169] If the capacity change rate at each temperature calculated by the above formula 2 was within ±15%, it was judged as O (pass), and if any one was not within ±15%, it was judged as × (fail), and these results are shown in Table 1 below.

[0170] [Table 1]

[0171] Referring to Table 1, Examples 1 to 9, in which the Ge content in the multilayer ceramic capacitor is 0.01 moles to 20 moles per 100 moles of Ti, have higher capacitance than Comparative Example 1 and a higher MTTF value than Comparative Example 1, which indicates that the capacitors have high reliability and excellent temperature characteristics.

[0172] In contrast, in the case of Comparative Example 1 in which the Ge content in the multilayer ceramic capacitor is less than 0.01 moles per 100 moles of Ti, it can be confirmed that the capacitance characteristics, reliability, and temperature characteristics are all inferior to those of the embodiment.

[0173] In addition, in the case of Comparative Examples 2 and 3, in which the Ge content in the multilayer ceramic capacitor exceeds 20 moles per 100 moles of Ti, the MTTF value is lower than that of the embodiment, confirming that the reliability of the capacitor is inferior.

[0174] [Table 2]

[0175] [Table 3]

[0176] Referring to Tables 1 and 3, it can be seen that the multilayer ceramic capacitors according to Examples 1 and 2 have X / Y values ​​of 1 or more, and thus the capacitance characteristics, reliability, and temperature characteristics of the capacitors are all excellent.

[0177] Although the preferred embodiment of the present invention has been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims, the detailed description of the invention, and the accompanying drawings, and it is natural that these also fall within the scope of the present invention. [Explanation of symbols]

[0178] 100: Multilayer ceramic capacitor 110: Capacitor Body 111: Dielectric layer 112, 113: Coverage area 121: 1st internal electrode 122:Second internal electrode 131: 1st external electrode 132:Second external electrode

Claims

1. A multilayer ceramic capacitor including a capacitor body including a dielectric layer and an internal electrode, and an external electrode disposed on an outer side of the capacitor body, The multilayer ceramic capacitor contains Ti and Ge, In the multilayer ceramic capacitor, the content of Ge relative to 100 moles of Ti is 0.01 mole to 20 moles.

2. the dielectric layer contains the Ti and the Ge, the internal electrode contains the Ni and the Ge, The average content (mol) of Ge relative to 100 mol of Ni in the internal electrode is represented by X, When the average content (mol) of Ge relative to 100 mol of Ti in the dielectric layer is Y, The relationship between the X and the Y is expressed by the following formula 1: [Formula 1] X / Y≧1 The multilayer ceramic capacitor according to claim 1 , which satisfies the above.

3. 3. The multilayer ceramic capacitor according to claim 2, wherein X is 0.1 to 15 moles.

4. 3. The multilayer ceramic capacitor according to claim 2, wherein Y is 0.05 to 10 moles.

5. the dielectric layer includes a plurality of dielectric crystal grains and a grain boundary between at least two of the dielectric crystal grains, the dielectric crystal grains include 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 2. The multilayer ceramic capacitor of claim 1, comprising: (0.995≦m≦1.010, 0≦x≦0.10, 0<y≦0.20), or a combination thereof.

6. 6. The multilayer ceramic capacitor according to claim 5, wherein the minor components include Ge, Dy, V, Mn, Cr, Si, Al, Mg, Sn, Sb, Ga, In, Ba, La, Y, Ac, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb, Lu, Hf, or a combination thereof.

7. 2. The multilayer ceramic capacitor according to claim 1, wherein the internal electrodes have an average thickness of 0.05 to 2 [mu]m.

8. 2. The multilayer ceramic capacitor according to claim 1, wherein the dielectric layers have an average thickness of 0.05 μm to 10 μm.

9. A multilayer ceramic capacitor including a capacitor body including a dielectric layer and an internal electrode, and an external electrode disposed on an outer side of the capacitor body, The multilayer ceramic capacitor contains Ti and Ge, In the multilayer ceramic capacitor, the content of Ge relative to 100 moles of Ti is 0.01 mole to 20 moles, the dielectric layer includes a plurality of dielectric crystal grains and a grain boundary between at least two of the dielectric crystal grains, The multilayer ceramic capacitor, wherein the grain boundaries include Ge, Ge oxide, or a combination thereof.

10. the dielectric crystal grains include 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 10. The multilayer ceramic capacitor of claim 9, comprising: (0.995≦m≦1.010, 0≦x≦0.10, 0<y≦0.20), or a combination thereof.

11. The multilayer ceramic capacitor according to claim 10, wherein the minor components include Ge, Zr, Mn, Cr, Si, Al, Mg, Sn, Sb, Hf, Ga, In, La, Y, Ac, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, or a combination thereof.

12. The multilayer ceramic capacitor according to claim 10 , wherein the dielectric grains further comprise Ge, Ge oxide, or a combination thereof.

13. The multilayer ceramic capacitor according to claim 9 , wherein the internal electrodes include a conductive metal and the Ge.

14. The multilayer ceramic capacitor according to claim 13 , wherein the internal electrodes contain an alloy of the conductive metal and the Ge.

15. the external electrode includes a sintered metal layer in contact with the capacitor body; The multilayer ceramic capacitor according to claim 9 , wherein the sintered metal layer includes a conductive metal and the Ge.

16. 10. The multilayer ceramic capacitor according to claim 9, wherein the internal electrodes have an average thickness of 0.05 μm to 2 μm.

17. 10. The multilayer ceramic capacitor according to claim 9, wherein the average thickness of the dielectric layers is 0.05 μm to 10 μm.

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