Multilayer ceramic electronic components

Abstract

To provide a multilayer ceramic electronic component, having improved moisture resistance reliability and high-temperature IR characteristics thereof, capable of preventing penetration of external moisture and a plating solution by improving coupling force between internal electrodes and external electrodes, and further capable of preventing occurrence of cracking due to excessive formation of an alloy in internal electrodes.SOLUTION: One embodiment of the present invention may provide a multilayer ceramic electronic component including: a body including dielectric layers and a plurality of internal electrodes stacked with a respective one of the dielectric layers interposed therebetween and including a first metal; and external electrodes disposed outside the body and including a second metal, and at least some of the plurality of internal electrodes include a core-shell region including the first and second metals, and average contents of the second metal in a core portion and a shell portion of the core-shell region are different from each other.SELECTED DRAWING: Figure 5

Description

Technical Field

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

Background Art

[0002] A multilayer ceramic capacitor, which is one of multilayer ceramic electronic components (MULTILAYER CERAMIC ELECTRONIC COMPONENT), is a chip-shaped capacitor that is mounted on a printed circuit board of various electronic products such as video equipment such as a liquid crystal display (LCD) and a plasma display panel (PDP), a computer, a smartphone, and a mobile phone, and serves to charge or discharge electricity.

[0003] Such a multilayer ceramic capacitor can be used as a component of various electronic devices due to its advantages of being small while ensuring high capacitance and being easy to mount. As the functions of many electronic products in fields where high reliability is required are electronicized and the demand increases, high reliability is also required for multilayer ceramic capacitors. Factors that pose problems in the high reliability of such multilayer capacitors include the penetration of plating solution generated during the plating process, the occurrence of cracks due to external impact, and the penetration of moisture from the outside.

[0004] To solve such problems, conventionally, a multilayer ceramic capacitor has been developed in which a nickel (Ni)-copper (Cu) alloy region is formed at an end portion of an internal electrode that is connected to an external electrode to improve the bonding force between the internal electrode and the external electrode and prevent the penetration of moisture and plating solution.

[0005] However, if the alloy region is formed excessively, radial cracks occur due to the volume expansion of the internal electrodes, and problems such as a decrease in bending strength and moisture penetration through the cracks still remain. Therefore, there is a need to develop multilayer ceramic capacitors that prevent excessive volume expansion of the internal electrodes and have improved moisture resistance reliability. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Korean Published Patent Publication No. 10-2016-0110123 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] One of the various objectives of the present invention is to improve the moisture resistance reliability and high-temperature IR characteristics of multilayer ceramic electronic components.

[0008] One of the various objectives of the present invention is to improve the bonding force between the internal electrode and the external electrode to prevent the penetration of moisture and plating solution from the outside.

[0009] One of the various objectives of the present invention is to prevent the occurrence of cracks in the internal electrodes due to excessive alloy formation.

[0010] However, the objectives of the present invention are not limited to those described above and can be more easily understood in the process of describing specific embodiments of the present invention. [Means for solving the problem]

[0011] One embodiment of the present invention provides a multilayer ceramic electronic component comprising a body including a dielectric layer and a plurality of internal electrodes containing a first metal, laminated with the dielectric layer in between, and an external electrode disposed outside the body and containing a second metal, wherein at least a portion of the plurality of internal electrodes includes a core-shell region containing the first and second metals, and the core portion and shell portion of the core-shell region have different average content of the second metal. [Effects of the Invention]

[0012] One of the various effects of the present invention is to improve the moisture resistance reliability and high-temperature IR characteristics of multilayer ceramic electronic components.

[0013] One of the various effects of the present invention is to improve the bonding force between the internal electrode and the external electrode, thereby preventing the penetration of moisture and plating solution from the outside.

[0014] One of the various effects of this invention is to prevent the occurrence of cracks in the internal electrodes due to excessive alloy formation. [Brief explanation of the drawing]

[0015] [Figure 1] This is a schematic perspective view of a multilayer ceramic electronic component according to one embodiment of the present invention. [Figure 2] This is a schematic perspective view showing the main body of a multilayer ceramic electronic component. [Figure 3] This is a schematic cross-sectional view showing a section along line I-I' in Figure 1. [Figure 4] This is a schematic cross-sectional view showing a section along line II-II' in Figure 1. [Figure 5] This is an enlarged view showing area B in Figure 3. [Figure 6] This diagram schematically shows the core-shell region of the internal electrode. [Figure 7]This is an image obtained by STEM-EDS (Scanning transmission electron microscopy-Energy dispersive x-ray spectroscopy) analysis of the internal electrode in the region connected to the external electrode. [Figure 8] This is a graph showing the results of EDS line profile analysis that analyzes the core-shell region of FIG. 7 in the dotted line direction and shows the detected amount of copper (Cu). [Figure 9] This is a graph showing the results of EDS line profile analysis that analyzes the alloy region of FIG. 7 in the dotted line direction and shows the detected amount of copper (Cu). [Figure 10] This is a graph showing the results of the moisture resistance reliability test according to the embodiment. [Figure 11] This is a graph showing the results of the moisture resistance reliability test according to the comparative example.

Best Mode for Carrying Out the Invention

[0016] Hereinafter, embodiments of the present invention will be described with reference to specific embodiments and the accompanying drawings. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Also, the embodiments of the present invention are provided to more fully explain the present invention to an ordinary technician. Therefore, the shapes and sizes of elements in the drawings may be enlarged or reduced (or emphasized or simplified) for a clearer explanation, and elements denoted by the same reference numerals in the drawings are the same elements.

[0017] In order to clearly describe the present invention in the drawings, parts not related to the description are omitted, and the sizes and thicknesses of each component shown in the drawings are arbitrarily shown for convenience of description. Therefore, the present invention is not necessarily limited to what is shown in the drawings. For components having the same function within the scope of the same concept, the same reference numerals are used for description. Further, throughout the specification, when a certain part "includes" a certain component, this means that other components can be further included, rather than excluding other components, unless there is a particularly contrary description.

[0018] In the drawings, the first direction can be defined as the length L direction, the second direction as the thickness T direction, and the third direction as the width W direction.

[0019] FIG. 1 is a perspective view schematically showing a multilayer ceramic electronic component according to an embodiment of the present invention, FIG. 2 is a perspective view schematically showing the main body of the multilayer ceramic electronic component, FIG. 3 is a cross-sectional view schematically showing a cut surface along I-I' of FIG. 1, FIG. 4 is a cross-sectional view schematically showing a cut surface along II-II' of FIG. 1, FIG. 5 is an enlarged view showing an enlarged B region of FIG. 3, and FIG. 6 schematically shows a core-shell region of an internal electrode.

[0020] Referring to FIGS. 1 to 6, a multilayer ceramic electronic component 100 according to an embodiment of the present invention includes a main body 110 in which a dielectric layer 111 and a plurality of internal electrodes 121, 122 including a first metal are laminated with the dielectric layer 111 interposed therebetween, and external electrodes 131, 132 disposed outside the main body 110 and including a second metal. At least a part of the plurality of internal electrodes 121, 122 includes a core-shell region 12 including the first and second metals, and the core portion 12a and the shell portion 12b of the core-shell region 12 can have different average contents of the second metal.

[0021] As mentioned above, when an alloy region is formed at the end of the internal electrode that connects to the external electrode in order to improve the moisture resistance reliability of multilayer ceramic electronic components, the volume expansion of the internal electrode can cause radial cracks, and moisture may penetrate from the outside through these cracks.

[0022] In contrast, the multilayer ceramic electronic component 100 according to one embodiment of the present invention improves the moisture resistance reliability of the multilayer ceramic electronic component 100 by including at least a portion of the plurality of internal electrodes 121 and 122 in a core-shell region 12 containing the first and second metals, while preventing radial cracks due to volume expansion of the internal electrodes 121 and 122.

[0023] The following describes in more detail each component included in the multilayer ceramic electronic component 100 according to one embodiment of the present invention.

[0024] There are no particular limitations on the specific shape of the main body 110, but as shown in the figure, the main body 110 can be a hexahedron or a similar shape. Due to the shrinkage of the ceramic powder contained in the main body 110 during the firing process and the polishing of the corners, the main body 110 may not be a perfectly straight hexahedron, but it may be substantially hexahedron-shaped.

[0025] The main body 110 may have a first surface 1 and a second surface 2 facing each other in a first direction, a third surface 3 and a fourth surface 4 connected to the first surface 1 and the second surface 2 and facing each other in a second direction, and a fifth surface 5 and a sixth surface 6 connected to the first surface 1, the second surface 2, the third surface 3 and the fourth surface 4 and facing each other in a third direction.

[0026] The main body 110 can be constructed by alternately stacking dielectric layers 111 and internal electrodes 121 and 122. The multiple dielectric layers 111 forming the main body 110 are in a fired state, and the boundaries between adjacent dielectric layers 111 can be integrated to such an extent that they are difficult to confirm without using a scanning electron microscope (SEM).

[0027] The dielectric layer 111 can be formed by firing a ceramic green sheet containing ceramic powder, an organic solvent, and a binder. The ceramic powder is not particularly limited as long as sufficient capacitance can be obtained, but for example, barium titanate (BaTiO3) material, strontium titanate (SrTiO3) material, etc. can be used, however the present invention is not limited thereto.

[0028] In this case, the thickness of the dielectric layer 111 can be 10 μm or less, taking into consideration the size and capacitance of the main body 110, and can be 0.6 μm or less, more preferably 0.4 μm or less, in order to miniaturize and increase the capacitance of the ceramic electronic component 100, but the present invention is not limited thereto.

[0029] Here, the thickness of the dielectric layer 111 can refer to the average thickness of the dielectric layer 111 placed between the internal electrodes 121 and 122. The average thickness of the dielectric layer 111 can be measured by scanning the cross-sections of the main body 110 in the first and second directions using a scanning electron microscope at 10,000x magnification. More specifically, the thickness of any dielectric layer 111 can be measured at multiple points, for example, 30 points equally spaced in the first direction, and the average value can be obtained. Furthermore, by extending such average value measurements to a large number of dielectric layers 111, the average thickness of the dielectric layer 111 can be further generalized.

[0030] The main body 110 may include a capacitance forming section Ac disposed inside the main body 110 and comprising a plurality of first internal electrodes 121 and a plurality of second internal electrodes 122 arranged facing each other with a dielectric layer 111 in between, thereby forming a capacitance; a first cover section 112 disposed above the capacitance forming section Ac; and a second cover section 113 disposed below the capacitance forming section Ac.

[0031] The cover portions 112 and 113 can be formed by stacking a single dielectric layer or two or more dielectric layers in a second direction on the upper and lower surfaces of the capacitance forming portion Ac, respectively, and can essentially serve to prevent damage to the internal electrodes due to physical or chemical stress. The cover portions 112 and 113 can have the same configuration as the dielectric layer 111, except that they do not include the internal electrodes. The average thickness of the cover portions 112 and 113 can be 20 μm or less, but the present invention is not limited thereto. The thickness of the cover portions 112 and 113 refers to the length of the cover portions 112 and 113 in the second direction, and can refer to the average value of the thickness measured at 30 points that are equally spaced in the first direction in the cross-sections of the main body 110 in the first and second directions.

[0032] The main body 110 may include margin portions 114 and 115 positioned on the sides of the capacitance forming portion Ac with respect to the third direction. The margin portions 114 and 115 may include a first margin portion 114 positioned on the fifth surface 5 of the main body 110 and a second margin portion 115 positioned on the sixth surface 6. The margin portions 114 and 115 may represent the regions between the interface between both ends of the internal electrodes 121 and 122 and the main body 110 in cross-sections obtained by cutting the main body 110 in the second and third directions. The margin portions 114 and 115 can essentially serve to prevent damage to the internal electrodes 121 and 122 due to physical or chemical stress. The margin portions 114 and 115 may include the same or different materials as the dielectric layer 111.

[0033] The margin portions 114 and 115 can be formed by applying conductive paste to the ceramic green sheet, except where the margin portions are formed, to create internal electrodes. Alternatively, in order to suppress the step caused by the internal electrodes 121 and 122, after lamination the sheet is cut so that the internal electrodes 121 and 122 are exposed on the fifth and sixth surfaces 5 and 6 of the main body, and then a single dielectric layer or two or more dielectric layers are laminated on both sides of the capacitance forming portion Ac in the third direction to form the margin portions 114 and 115. The average thickness of the margin portions 114 and 115 can be 20 μm or less, but the present invention is not limited thereto. The thickness of the margin portions 114 and 115 means the length of the margin portions 114 and 115 in the third direction, and can mean the average value of the thickness measured at 30 points that are equally spaced in the second direction in the second and third direction cross-sections of the main body 110.

[0034] The internal electrodes 121 and 122 can be arranged alternately with the dielectric layer 111, and a plurality of first internal electrodes 121 and a plurality of second internal electrodes 122 can be arranged facing each other with the dielectric layer 111 in between. That is, the first and second internal electrodes 121 and 122 are pairs of electrodes having different polarities and can be formed to be alternately exposed on the first surface 1 and the second surface 2 of the main body 110 along the stacking direction of the dielectric layer 111. For example, each of the plurality of first internal electrodes 121 can be exposed on the first surface 1 while separated from the second surface 2. Also, each of the plurality of second internal electrodes 122 can be exposed on the second surface 2 while separated from the first surface 1. The plurality of first internal electrodes 121 and the plurality of second internal electrodes 122 can be electrically isolated from each other by the dielectric layer 111 arranged between them. The multiple first internal electrodes 121 and the multiple second internal electrodes 122 can be stacked alternately in the second direction, but are not limited to this, and may also be stacked alternately in the third direction.

[0035] The internal electrodes 121 and 122 can be formed by printing a conductive paste for internal electrodes containing a first metal to a predetermined thickness onto a ceramic green sheet. While screen printing or gravure printing can be used as the printing method for the conductive paste for internal electrodes, the present invention is not limited thereto.

[0036] The first metal contained in the internal electrodes 121 and 122 may include one or more of the following: nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), gold (Au), platinum (Pt), tin (Sn), tungsten (W), titanium (Ti), and alloys thereof, and more preferably nickel (Ni).

[0037] In this case, the thickness of the internal electrodes 121 and 122 can be 10 μm or less, taking into consideration the size and capacitance of the main body 110, and can be 0.8 μm or less, more preferably 0.4 μm or less, in order to miniaturize and increase the capacitance of the multilayer ceramic electronic component 100, but the present invention is not limited thereto.

[0038] Here, the thickness of internal electrodes 121 and 122 can refer to the average thickness of internal electrodes 121 and 122. The average thickness of internal electrodes 121 and 122 can be measured by scanning the cross-sections of the main body 110 in the first and second directions using a scanning electron microscope at 10,000x magnification. More specifically, the thickness of any internal electrode can be measured at multiple points, for example, 30 points equally spaced in the first direction, and the average value can be calculated. By extending this measurement of average values ​​to a large number of internal electrodes, the average thickness of the internal electrodes can be further generalized.

[0039] External electrodes 131 and 132 are positioned on the first surface 1 and second surface 2 of the main body 110 and can extend to parts of the third surface 3, fourth surface 4, fifth surface 5, and sixth surface 6, respectively. The external electrodes 131 and 132 may include first external electrodes 131 and second external electrodes 132 that are connected to a plurality of first internal electrodes 121 and a plurality of second internal electrodes 122, respectively.

[0040] The external electrodes 131 and 132 contain a second metal, and the second metal contained in the external electrodes 131 and 132 may include one or more of the following: copper (Cu), nickel (Ni), palladium (Pd), platinum (Pt), gold (Au), silver (Ag), lead (Pb), and alloys thereof, and more preferably, copper (Cu).

[0041] The external electrodes 131 and 132 can be formed by dipping the first surface 1 and second surface 2 of the main body 110 into a conductive paste for external electrodes containing the second metal powder and glass, and then firing it. Alternatively, they may be formed by transferring a sheet containing conductive metal and glass. In this way, the external electrodes 131 and 132 can be fired electrodes containing conductive metal and glass.

[0042] The drawing illustrates a multilayer ceramic electronic component 100 having two external electrodes 131 and 132, but it is not limited to this, and the number and shape of the external electrodes 131 and 132 can be changed according to the shape of the internal electrodes 121 and 122 or other purposes.

[0043] Figure 5 shows an enlarged view of a portion of the first internal electrode 121 and the first external electrode 131. The configuration is similar, except that the first external electrode 131 is connected to the first internal electrode 121 and the second external electrode 132 is connected to the second internal electrode 122. Therefore, the following explanation will be based on the first internal electrode 121 and the first external electrode 131, but this will also include the explanation for the second internal electrode 122 and the second external electrode 132.

[0044] At least some of the multiple internal electrodes 121 may include a core-shell region 12 containing the first and second metals. That is, the core-shell region 12 may include a core portion 12a and a shell portion 12b surrounding the core portion 12a.

[0045] The shell portion 12b can be defined as a region where the content of the second metal is 2 at% or more, and the core portion 12a can be defined as the region surrounded by the shell portion 12b. In this case, the content of the second metal in the core portion 12a may be less than 2 at%. The content (at%) of the second metal can be measured by mapping the second metal in the first and second cross-sections of the main body 110 by STEM-EDS analysis and by the line profile of the core-shell region 12.

[0046] The average content of the second metal can differ between the core portion 12a and the shell portion 12b. The average content of the second metal in the shell portion 12b can be derived as the average value of the data from four points, by measuring the content (at%) of the second metal at each of points P1 to P4 in any core-shell region 12. Similarly, the average content of the second metal in the core portion 12a can be derived as the average value of the data from four points, by measuring the content (at%) of the second metal at each of points P5 to P8 in any core-shell region 12. As described above, the content of the second metal can be measured by STEM-EDS (Scanning Transmission Electron Microscopy-Energy Dispersive X-ray Spectroscopy) and line-profile in the first and second cross-sections of the main body 110.

[0047] In this case, the shell portion 12b can have a higher average content of the second metal than the core portion 12a. For example, if the first metal contains nickel (Ni) and the second metal contains copper (Cu), the shell portion 12b can have a higher average content of copper (Cu) than the core portion 12a. By having at least a portion of the multiple internal electrodes 121 include the core-shell region 12, the moisture resistance reliability of the multilayer ceramic electronic component 100 can be improved and radiative cracks due to volume expansion of the internal electrodes 121 can be prevented without forming an excessive alloy region. That is, the moisture resistance reliability of the multilayer ceramic electronic component 100 can be improved by the shell portion 12b with a high content of the second metal, and the second metal content of the core portion 12a, which is thicker than the shell portion 12b, can be lower, thus preventing the occurrence of cracks due to volume expansion of the internal electrodes 121.

[0048] The core-shell region 12 can be formed by the diffusion of the second metal towards the internal electrodes 121 and 122 during the process of applying the conductive paste for the external electrodes to the main body 110 and firing it. As a result, the core-shell region 12 can be formed in a region within 1 μm to 10 μm from the interface between the internal electrode 121 and the external electrode 131. Since the core-shell region 12 is formed by diffusion, at least some of the multiple internal electrodes 121 may contain multiple core-shell regions 12. Furthermore, due to the diffusion of the second metal, at least some of the multiple internal electrodes 121 may contain alloy regions 12c of the first and second metals. This further improves the moisture resistance reliability of the multilayer ceramic electronic component 100.

[0049] If the firing temperature of the external electrode 131 is too high, an excessive amount of alloy region 12c may be formed. This can cause the volume of the internal electrode 121 to expand, potentially leading to the formation of radial cracks in the main body 110. Conversely, if the firing temperature is too low, the core-shell region 12 may not be formed. Therefore, the firing temperature can be set between 700°C and 900°C, but the present invention is not limited to this range.

[0050] Furthermore, in the cross-sections of the multilayer ceramic electronic component 100 in the first and second directions, the core-shell region 12 can be easily formed by ensuring that the length of the interface where the external electrode 131 and the internal electrode 121 are in contact, that is, the ratio of the second direction length covered by the glass in the second direction length of the first and second surfaces 1 and 2 of the main body 110 (hereinafter defined as glass coverage), is 2% to 33%, but the present invention is not limited thereto.

[0051] When the above glass coverage satisfies 2% to 33%, the second metal does not diffuse into the center of the internal electrode 121 in the thickness direction, but rather diffuses through the interface between the internal electrode 121 and the dielectric layer 111, thereby forming a core-shell region 12.

[0052] If the proportion of the length covered by the glass is less than 2%, an excessive amount of alloy region 12c may be formed. This may cause radial cracks due to volume expansion of the internal electrode 121. If the proportion of the length covered by the glass exceeds 33%, the glass may prevent the diffusion of the second metal, and the core-shell region 12 may not be formed. This may reduce the moisture resistance and high-temperature insulation resistance reliability.

[0053] Here, the glass may have a composition of mixed oxides, and may contain transition metal oxides such as zinc (Zn) and / or alkaline earth metal oxides such as calcium (Ca), but the present invention is not limited thereto. In this case, in order to adjust the glass coverage, the glass softening point may be 600°C to 700°C, and in order to adjust the softening point, the glass may contain one or more of ZnO, BaO, B2O3, SiO2, CaO, Al2O3, Li2O, K2O, and V2O5, but the present invention is not limited thereto.

[0054] The glass content in the conductive paste for external electrodes can be 1% to 20% by weight relative to 100% by weight of the second metal powder, but the present invention is not limited thereto and can be changed depending on the composition of the conductive paste for external electrodes and the firing conditions.

[0055] In one embodiment, the core-shell region 12 may have a gradient of the second metal content. For example, as you move away from the core portion 12a in the thickness direction of the internal electrode 121, the second metal content in the shell portion 12b may increase and then decrease. This allows the point where the second metal content is maximum in the shell portion 12b to be formed in the center of the shell portion 12b in the thickness direction. That is, the shell portion 12b may have a peak value for the second metal content.

[0056] In one embodiment, the maximum value of the second metal content in the shell portion 12b can be 3 at% to 20 at%. In one embodiment, the minimum value of the second metal content in the core portion 12a can be 1 at% to 1.5 at%. Furthermore, in one embodiment, the ratio of the maximum value of the second metal content in the shell portion 12b to the minimum value of the second metal content in the core portion 12a in any core-shell region 12 can satisfy 3.0 to 14.2.

[0057] Therefore, the shell portion 12b, which has a high content of the second metal, improves the moisture resistance reliability of the multilayer ceramic electronic component 100, while the core portion 12a, which has a low content of the second metal, minimizes the volume expansion of the internal electrode 121 and prevents the occurrence of cracks.

[0058] In one embodiment of the present invention, the ratio of the thickness T2 of the shell portion 12b to the thickness T1 of the internal electrode 121 can satisfy 0.12 to 0.23. In this case, the thickness of the internal electrode 121 can be measured by STEM-EDS analysis of the first and second cross-sections of the main body 110. The thickness of the shell portion 12b can mean the length from the point where the content of the second metal, which appears as you move away from the center of the core portion 12a, becomes 2 at%, after measuring the gradient of the second metal content by the EDS line-profile of the core-shell region 12, to another point where the content of the second metal, which appears as you move further away from the center of the core portion 12a, becomes 2 at%. In this case, the thickness T2 of the shell portion 12b can be, for example, 70 nm to 150 nm, but the present invention is not limited thereto.

[0059] In one embodiment of the present invention, the external electrodes 131 and 132 may include first electrode layers 131a and 132a disposed on the main body 110 and containing the second metal, and second electrode layers 131b and 132b disposed on the first electrode layers 131a and 132a and containing a third metal. In this case, the first electrode layers 131a and 132a may be fired electrodes containing the second metal and glass. The first electrode layers 131a and 132a can be formed by dipping them in a conductive paste for external electrodes containing the second metal powder and glass, and then firing them.

[0060] The second electrode layers 131b and 132b can improve mounting characteristics. The type of the second electrode layers 131b and 132b is not particularly limited and can be a plating layer containing nickel (Ni), tin (Sn), palladium (Pd), and / or alloys containing these as the third metal, and may consist of multiple layers. The second electrode layers 131b and 132b can be, for example, a nickel (Ni) plating layer or a tin (Sn) plating layer, and may be formed in a manner in which a nickel (Ni) plating layer and a tin (Sn) plating layer are formed in sequence. Furthermore, the second electrode layers 131b and 132b may contain multiple nickel (Ni) plating layers and / or multiple tin (Sn) plating layers. Embodiment

[0061] An internal electrode pattern was formed by printing a conductive paste for internal electrodes containing nickel (Ni) powder as the first metal powder onto a ceramic green sheet, and then stacking the ceramic green sheets on which the internal electrode pattern was formed to create a ceramic laminate.

[0062] After firing the above ceramic laminate to form a main body 110 including a dielectric layer 111 and internal electrodes 121 and 122, the first surface 1 and second surface 2 of the main body 110 were dipped in a conductive paste for external electrodes containing copper (Cu) powder and glass as a second metal powder, and fired to form external electrodes 131 and 132.

[0063] Figure 7 shows an image obtained by STEM-EDS analysis of the internal electrodes in the region connected to the external electrodes. More specifically, it is an image obtained by mapping the copper (Cu) element to the internal electrodes 121 and 122 in the region connected to the external electrodes 131 and 132 in the first and second cross-sections of the main body 110 at a magnification of 9900x. In this case, the brighter the region, the higher the copper (Cu) element content.

[0064] Referring to Figure 7, the core-shell region 12 can be clearly distinguished from the shell portion 12b, which appears bright due to its high copper (Cu) content, and the core portion 12a, which appears dark due to its low copper (Cu) content. Furthermore, the alloy region 12c can be distinguished from the core-shell region 12 by the diffusion of copper (Cu) to the center of the internal electrodes 121 and 122 in the thickness direction.

[0065] Next, in Figure 7, the core-shell region 12 was subjected to line-profile analysis in the direction of the dotted line. Also in Figure 7, the alloy regions 12c of the first and second metals were subjected to line-profile analysis in the direction of the dotted line.

[0066] Figure 8 is a graph showing the EDS line profile analysis results, which analyze the core-shell region of Figure 7 in the direction of the dotted line and indicate the amount of copper (Cu) detected. Figure 9 is a graph showing the EDS line profile analysis results, which analyze the alloy region of Figure 7 in the direction of the dotted line and indicate the amount of copper (Cu) detected.

[0067] Referring to Figures 8 and 9, it can be seen that in the core-shell region 12, a peak in copper (Cu) content occurs in the shell portion 12b. This indicates that the shell portion 12b, which is the first to come into contact with moisture penetrating from the outside, has a high copper (Cu) content, improving moisture resistance reliability, while the thicker core portion 12a has a low copper (Cu) content, minimizing the volume expansion of the internal electrodes and preventing crack formation. Therefore, moisture resistance reliability can be improved together with the alloy region 12c, and furthermore, crack formation due to volume expansion of the internal electrodes can be prevented.

[0068] Based on the EDS line profile analysis results described above, in the core-shell region 12 located in the region where the distance from the interface between the external electrode and the internal electrode is 1 μm to 10 μm, the ratio of the thickness T2 of the shell portion 12b to the thickness T1 of the internal electrode, the maximum value of the secondary metal content of the shell portion 12b, the minimum value of the secondary metal content of the core portion 12a, and the ratio of the maximum value of the secondary metal content of the shell portion 12b to the minimum value of the secondary metal content of the core portion 12a were measured and are shown in Table 1 below. At this time, the values ​​measured from five samples prepared for each sample number were averaged and listed.

[0069] [Table 1]

[0070] Referring to Table 1, it can be seen that the thickness T2 of the shell portion 12b is 70 nm to 150 nm, and the ratio of the thickness T2 of the shell portion 12b to the thickness T1 of the internal electrode satisfies 0.12 to 0.23. Furthermore, it can be confirmed that the maximum copper (Cu) content of the shell portion 12b satisfies 3 at% to 20 at%, the minimum copper (Cu) content of the core portion 12a satisfies 1 at% to 1.5 at%, and the ratio of the maximum copper (Cu) content of the shell portion 12b to the minimum copper (Cu) content of the core portion 12a satisfies 3.0 to 14.2.

[0071] Humidity resistance reliability tests were performed on embodiments including an internal electrode with a core-shell region 12 formed on it, and comparative examples including an internal electrode without a core-shell region 12 and an alloy region 12c. For each of the 40 sample chips, the insulation resistance was measured while applying a rated voltage of 4V for 24 hours under conditions of 85% relative humidity and 85°C.

[0072] Figure 10 is a graph showing the results of a humidity resistance reliability test according to the embodiment. Figure 11 is a graph showing the results of a humidity resistance reliability test according to a comparative example. Referring to Figures 10 and 11, in the embodiment including an internal electrode in which the core-shell region 12 is formed, the insulation resistance of all samples except one sample is 10 8 It was confirmed that the insulation resistance remained above Ω. In contrast, in the comparative example, the insulation resistance of most samples was 10 8 It was confirmed that the reading was not maintained above Ω.

[0073] Although embodiments of the present invention have been described in detail above, the present invention is not limited by the embodiments described above and the accompanying drawings, but is limited by the claims provided herein. Therefore, within the scope of the technical idea of ​​the present invention as described in the claims, various forms of substitution, modification, and alteration are possible by persons with ordinary skill in the art, and these also fall within the scope of the present invention. [Explanation of Symbols]

[0074] 100 Multilayer Ceramic Electronic Components 110 Main Unit 111 Dielectric layer 112, 113 Cover section 114, 115 Margin section 121, 122 Internal electrode 131, 132 External electrode 131a, 132a 1st electrode layer 131b, 132b second electrode layer 12 Core-Shell Region 12a Core section 12b Shell section 12c alloy area

Claims

1. A dielectric layer and a body comprising a plurality of internal electrodes containing a first metal, which are laminated with the dielectric layer sandwiched in between, The external electrode, which is located on the outside of the main body and includes a second metal, At least a portion of the plurality of internal electrodes includes a core-shell region containing the first metal and the second metal, The core and shell portions of the core-shell region are multilayer ceramic electronic components in which the average content of the second metal differs from that of the other.

2. The multilayer ceramic electronic component according to claim 1, wherein the shell portion has a higher average content of the second metal than the core portion.

3. The multilayer ceramic electronic component according to claim 1, wherein the core-shell region is formed in a region within 1 to 10 μm from the interface between the internal electrode and the external electrode.

4. The multilayer ceramic electronic component according to claim 1, wherein the core-shell region has a gradient in the content of the second metal.

5. The multilayer ceramic electronic component according to claim 4, wherein the content of the second metal in the shell portion increases and then decreases as it moves away from the core portion in the thickness direction of the internal electrode.

6. The multilayer ceramic electronic component according to any one of claims 1 to 5, wherein at least a portion of the plurality of internal electrodes includes a plurality of core-shell regions.

7. The multilayer ceramic electronic component according to any one of claims 1 to 5, wherein at least a portion of the plurality of internal electrodes includes an alloy region of the first metal and the second metal.

8. The multilayer ceramic electronic component according to any one of claims 1 to 5, wherein the ratio of the thickness of the shell portion to the thickness of the internal electrode is 0.12 to 0.

23.

9. The multilayer ceramic electronic component according to any one of claims 1 to 5, wherein the maximum content of the second metal in the shell portion is 3 at% to 20 at%.

10. The multilayer ceramic electronic component according to any one of claims 1 to 5, wherein the minimum content of the second metal in the core portion is 1 at% to 1.5 at%.

11. The multilayer ceramic electronic component according to any one of claims 1 to 5, wherein the ratio of the maximum content of the second metal in the shell portion to the minimum content of the second metal in the core portion is 3.0 to 14.

2.

12. The multilayer ceramic electronic component according to any one of claims 1 to 5, wherein the first metal comprises nickel (Ni) and the second metal comprises copper (Cu).

13. The multilayer ceramic electronic component according to any one of claims 1 to 5, wherein the external electrode comprises a first electrode layer disposed on the main body and containing the second metal, and a second electrode layer disposed on the first electrode layer and containing the third metal.

14. The multilayer ceramic electronic component according to claim 13, wherein the second electrode layer has a multilayer structure comprising a first layer containing nickel (Ni) as the third metal and a second layer containing tin (Sn) as the third metal.

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