Multilayer ceramic electronic component

Abstract

The present disclosure provides a multilayer ceramic electronic component including a ceramic main body having dielectric layers and internal electrodes, an electrode layer connected to the internal electrodes, and a conductive resin layer disposed on the electrode layer and including a conductive metal, a metal having a melting point lower than a melting point of the conductive metal, a conductive carbon, and a base resin. A content of the conductive carbon included in the conductive resin layer is 0.1 parts by weight to 5.0 parts by weight based on 100 parts by weight of the conductive metal.

Description

[0001] This application is a divisional application of the invention patent application "Multilayer Ceramic Electronic Components" filed on September 18, 2020, with application number 202010985161.6. Technical Field

[0002] The present invention relates to a multilayer ceramic electronic component with high flexural strength and conductivity. Background Technology

[0003] A multilayer ceramic capacitor is a type of ceramic electronic component. A multilayer ceramic capacitor may include multiple dielectric layers, an inner electrode arranged opposite each other with the dielectric layers between them, and an outer electrode electrically connected to the inner electrode.

[0004] The inner and outer electrodes are typically made using a paste containing conductive metal powder.

[0005] Multilayer ceramic capacitors are widely used as components in mobile communication devices such as computers, personal digital assistants (PDAs), and mobile phones due to their small size, high capacitance, and ease of installation.

[0006] Furthermore, with the recent increase in industrial interest in electronic components, multilayer ceramic capacitors also require high reliability and high strength for use in automotive or infotainment systems.

[0007] In multilayer ceramic capacitors, a conductive resin layer is coated onto the outer electrode to withstand vibrations, physical shocks, and thermal shocks such as high temperature and high humidity from the vehicle body.

[0008] Polymer materials such as epoxy resins can be coated onto conductive resin layers to improve impact resistance, and metal powders can be mixed with polymer materials to achieve electrical properties.

[0009] Research is underway on single components such as copper (Cu), tin (Sn), nickel (Ni), and silver (Ag), or mixtures thereof, as metal powders, and active research is being conducted on Sn (low-melting-point metal powder).

[0010] In a recent study, Sn powder (a low-melting-point metal powder) and Cu powder (a high-melting-point metal powder) were used, and heat treatment was performed at a temperature greater than or equal to the melting point of Sn to form a Cu-Sn alloy. This improved the interfacial adhesion to the electrode layer disposed beneath the Cu-Sn alloy and enhanced electrical conductivity.

[0011] However, if the Sn content is high, the impact resistance of the conductive resin layer may be reduced due to the formation of a network between Sn particles.

[0012] Therefore, even with only a small amount of Sn, further research is needed to improve interfacial adhesion with the underlying electrode layer and enhance conductivity. Summary of the Invention

[0013] One aspect of this invention is to provide a multilayer ceramic electronic component with high flexural strength and conductivity.

[0014] According to one aspect of the present invention, a multilayer ceramic electronic component includes: a ceramic body having a dielectric layer and an inner electrode; an electrode layer connected to the inner electrode; and a conductive resin layer disposed on the electrode layer and comprising a conductive metal, a metal having a melting point lower than that of the conductive metal, conductive carbon, and a matrix resin. Based on 100 parts by weight of the conductive metal, the conductive carbon content in the conductive resin layer is from 0.1 parts by weight to 5.0 parts by weight.

[0015] According to another aspect of the present invention, a multilayer ceramic electronic component includes: a ceramic body having a dielectric layer and an inner electrode; an electrode layer connected to the inner electrode; and a conductive resin layer disposed on the electrode layer, comprising a conductive metal, a metal having a melting point lower than that of the conductive metal, conductive carbon, and a matrix resin. The composition of the conductive resin layer exhibits two peaks in Raman analysis of the conductive resin layer.

[0016] According to another aspect of the present invention, a multilayer ceramic electronic component includes: a ceramic body having a first internal electrode and a second internal electrode, the first internal electrode and the second internal electrode being alternately stacked and a dielectric layer therebetween; and a first external electrode and a second external electrode disposed on the outer surface of the ceramic body and respectively connected to the first internal electrode and the second internal electrode. Each of the first external electrode and the second external electrode includes a conductive resin layer, the conductive resin layer comprising a conductive metal, a metal having a melting point lower than that of the conductive metal, conductive carbon, and a matrix resin, and the content of the conductive carbon in the conductive resin layer is from 0.4 wt% to 5.0 wt% based on the weight of the conductive resin layer.

[0017] According to another aspect of the present invention, a multilayer ceramic electronic component includes: a ceramic body having a dielectric layer and an internal electrode; an electrode layer connected to the internal electrode; and a conductive resin layer disposed on the electrode layer, wherein the conductive resin layer comprises tin (Sn), a conductive metal having a melting point higher than that of tin (Sn), and a matrix resin, and the conductive resin layer further comprises graphene or carbon black. Based on 100 parts by weight of the conductive metal, the tin (Sn) content in the conductive resin layer is from 10 parts by weight to 50 parts by weight. Attached Figure Description

[0018] The above and other aspects, features and other advantages of this disclosure will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:

[0019] Figure 1 This is a perspective view showing a multilayer ceramic capacitor according to an embodiment of the present disclosure;

[0020] Figure 2 It is along Figure 1 A cross-sectional view taken from line A-A';

[0021] Figure 3 for Figure 2 A magnified view of region P in the image;

[0022] Figure 4 This is a schematic enlarged view showing graphene used in one construction as disclosed herein;

[0023] Figure 5 This is a graph showing the nuclear magnetic resonance (NMR) analysis results of an external electrode paste including graphene according to an embodiment of the present disclosure;

[0024] Figure 6 This is a graph showing the Raman analysis results of a conductive resin layer including graphene according to an embodiment of the present disclosure; and

[0025] Figure 7 This is a cross-sectional view based on an additional embodiment. Detailed Implementation

[0026] In the following description, embodiments of the present disclosure will be described with reference to the accompanying drawings.

[0027] However, this disclosure may be exemplified in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of this disclosure to those skilled in the art.

[0028] Throughout this specification, it will be understood that when an element (such as a layer, region, or wafer (substrate)) is referred to as being "on" another element, "connected to" another element, or "bonded to" another element, the element may be directly "on" another element, "connected to" another element, or "bonded to" another element, or other elements may be present in between. In contrast, when an element is referred to as being "directly on" another element, "directly connected to" another element, or "directly bonded to" another element, no elements or layers may be present in between. Similar notations always indicate similar elements. As used herein, the term "and / or" includes any combination and all combinations of one or more of the associated listed items.

[0029] It will be apparent that although the terms first, second, third, etc., may be used herein to describe various components, assemblies, regions, layers, and / or parts, these components, assemblies, regions, layers, and / or parts should not be limited to these terms. These terms are used only to distinguish one component, assembly, region, layer, or part from another component, assembly, region, layer, or part. Therefore, without departing from the teachings of the exemplary embodiments, the first component, first assembly, first region, first layer, or first part discussed below may be referred to as a second component, second assembly, second region, second layer, or second part.

[0030] For ease of description, spatial relative terms such as “above,” “above,” “below,” and “under” are used herein to describe the positional relationship of one element to another in the orientation shown in the accompanying drawings. It will be understood that the spatial relative terms are intended to include not only the orientation depicted in the drawings but also different orientations of the device in use or operation. Similarly, if the device in the drawings is flipped, an element described as “above” or “above” relative to other elements or features would then be positioned as “below” or “under” relative to said other elements or features. Thus, the term “above” may include both above and below orientations depending on the specific orientation of the device or drawing. The device and drawing may be otherwise positioned (rotated 90 degrees or in other orientations), and the spatial relative descriptors used herein will be interpreted accordingly.

[0031] The terminology used herein describes particular embodiments only, and this disclosure is not limited thereto. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. It will be further understood that, when used in this specification, the terms “comprising” and / or “including” enumerate the presence of the stated features, integrals, steps, operations, components, elements, and / or groups thereof, but do not exclude the presence or addition of one or more other features, integrals, steps, operations, components, elements, and / or groups thereof.

[0032] In the following description, embodiments of the present disclosure will be illustrated with reference to schematic diagrams in the accompanying drawings. In manufacturing apparatus, variations in the shape of the apparatus can be predicted relative to the shape shown in the drawings, for example, due to manufacturing techniques and / or tolerances. Therefore, embodiments of the present disclosure should not be construed as limited to specific shapes in the areas shown herein, but can be interpreted more generally as including changes in shape due to manufacturing processes or tolerances. The following embodiments may also be constituted by one or a combination thereof.

[0033] The contents of this disclosure described below may have various configurations, and only illustrative configurations are shown and described herein, but this disclosure is not limited thereto.

[0034] Preferred embodiments of this disclosure will now be described with reference to the accompanying drawings.

[0035] Figure 1 This is a perspective view showing a multilayer ceramic capacitor according to an embodiment of the present disclosure.

[0036] Figure 2 It is along Figure 1 A cross-sectional view taken from line A-A'.

[0037] Figure 3 yes Figure 2 A magnified view of region P.

[0038] Reference Figures 1 to 3 According to an embodiment of the present disclosure, a multilayer ceramic electronic component 100 includes: a ceramic body 110 including a dielectric layer 111 and inner electrodes 121 and 122; electrode layers 131a and 131b connected to the inner electrodes 121 and 122; and conductive resin layers 132a and 132b formed on the electrode layers 131a and 131b and including a conductive metal 32a, a metal 32b having a melting point lower than that of the conductive metal 32a, conductive carbon 32c, and a matrix resin 32d.

[0039] In detail, the multilayer ceramic electronic component includes: a ceramic body 110, including a dielectric layer 111, a first internal electrode 121 and a second internal electrode 122, wherein the first internal electrode 121 and the second internal electrode 122 are alternately stacked in the ceramic body 110 and the dielectric layer 111 is located between the first internal electrode 121 and the second internal electrode 122; a first electrode layer 131a electrically connected to the first internal electrode 121; a second electrode layer 131b electrically connected to the second internal electrode 122; a first conductive resin layer 132a formed on the first electrode layer 131a; and a second conductive resin layer 132b formed on the second electrode layer 131b, wherein both the first conductive resin layer 132a and the second conductive resin layer 132b include a conductive metal 32a, a metal 32b having a melting point lower than that of the conductive metal 32a, conductive carbon 32c, and a matrix resin 32d.

[0040] The first conductive resin layer 132a and the second conductive resin layer 132b are formed by coating an external electrode paste comprising a conductive metal 32a, a metal 32b having a melting point lower than that of the conductive metal 32a, conductive carbon 32c and a matrix resin 32d, and the content of conductive carbon 32c contained in 100 parts by weight is from 0.1 parts by weight to 5.0 parts by weight (e.g., 0.5 parts by weight).

[0041] The metal 32b having a lower melting point than the conductive metal 32a may be tin (Sn), and the content of tin (Sn) contained in 100 parts by weight of conductive metal 32a may be from 10 parts by weight to 50 parts by weight.

[0042] Furthermore, conductive carbon 32c can be at least one of graphene, carbon nanotubes, and carbon black. In particular, conductive carbon 32c can be graphene.

[0043] Metal 32b and conductive carbon 32c, which have melting points lower than those of conductive metal 32a, will be described later.

[0044] There are no particular limitations on the matrix resin 32d, as long as it provides bonding properties and shock absorption and the matrix resin is mixed with the powder of the conductive metal 32a to form a paste, and the matrix resin 32d may include, for example, an epoxy resin.

[0045] Based on 100 parts by weight of conductive metal, the content of matrix resin 32d may be from 5 parts by weight to 30 parts by weight.

[0046] If the content of the base resin 32d is less than 5 parts by weight, the paste manufacturing operation may be difficult to perform due to insufficient resin, the phase stability may be reduced, leading to viscosity changes or phase separation during standing, the metal dispersibility may be reduced, resulting in a lower filling rate and potentially a decrease in density. If the content of the base resin 32d exceeds 30 parts by weight, the excessive amount of resin will reduce the metal-to-metal contact, leading to an increase in resistivity and an increase in the resin area on the surface. Therefore, when a plating layer is formed on the first conductive resin layer 132a and the second conductive resin layer 132b, incomplete plating may occur.

[0047] According to existing technology, in multilayer ceramic capacitors used in electrical or electronic devices, a conductive resin layer is applied to the outer electrode to withstand vibrations, physical shocks, and thermal shocks such as high temperature and high humidity.

[0048] Typically, when a conductive resin layer is disposed in the outer electrode of a multilayer ceramic capacitor, the conductive resin layer is manufactured to cover the entire electrode layer electrically connected to the inner electrode, so that current flows through the conductive resin layer to conduct electricity with the outside.

[0049] The conductive resin layer can be formed by including a conductive metal to ensure conductivity and a base resin to absorb vibrations. When the conductive resin layer includes a base resin, its durability against external stimuli, such as warping of multilayer ceramic electronic components, can be improved.

[0050] Polymer materials such as epoxy resin are applied to the conductive resin layer to improve impact resistance, and metal powder is mixed with the polymer material to achieve conductive properties.

[0051] Research is underway on single components such as Cu, Sn, Ni, Ag, or mixtures thereof as metal powders, and active research is being conducted on Sn (low melting point metal powder).

[0052] In a recent study, Sn powder, a metal powder with a low melting point, and Cu powder, a metal powder with a high melting point (e.g., higher than that of Sn powder), were used. Heat treatment was performed at a temperature greater than or equal to the melting point of Sn to form a Cu-Sn alloy. This improved interfacial adhesion with the underlying electrode layer and enhanced electrical conductivity.

[0053] However, if the Sn content is high, the impact resistance of the conductive resin layer may be reduced due to the formation of a network between Sn particles.

[0054] However, according to embodiments of this disclosure, both the first conductive resin layer 132a and the second conductive resin layer 132b comprise a conductive metal 32a, a metal 32b having a melting point lower than that of the conductive metal 32a, conductive carbon 32c, and a matrix resin 32d, and the content of conductive carbon 32c is from 0.1 parts by weight to 5.0 parts by weight per 100 parts by weight of conductive metal 32a. Therefore, even when only a small amount of Sn is contained, the flexural strength can be improved, and a multilayer ceramic electronic component with high conductivity can be realized.

[0055] In other words, the metal 32b, which has a lower melting point than the conductive metal 32a, can be tin (Sn), and the content of tin (Sn) contained in 100 parts by weight of conductive metal 32a can be from 10 parts by weight to 50 parts by weight.

[0056] Furthermore, conductive carbon 32c can be at least one of graphene, carbon nanotubes, and carbon black. In particular, conductive carbon 32c can be graphene.

[0057] In detail, based on 100 parts by weight of conductive metal 32a, the first conductive resin layer 132a and the second conductive resin layer 132b include 0.1 parts by weight to 5.0 parts by weight of conductive carbon 32c, thereby improving the bending strength of the multilayer ceramic capacitor according to the embodiments of the present disclosure and also improving the conductivity.

[0058] If the content of conductive carbon 32c is less than 0.1 parts by weight, multilayer ceramic electronic components with low equivalent series resistance cannot be achieved, and the impact resistance may be reduced due to the formation of a network between Sn.

[0059] Furthermore, if the content of conductive carbon 32c exceeds 5.0 parts by weight, during the formation of the coating on the upper part of the first conductive resin layer 132a and the second conductive resin layer 132b, uncoated defects or reduced fixation strength may occur.

[0060] When the content of conductive carbon 32c is calculated based on the weight of the conductive resin layer, the content of conductive carbon 32c is approximately 0.4 wt% to approximately 5.0 wt% of the conductive resin layer. In this case, if the content of conductive carbon 32c is less than 0.4 wt%, a multilayer ceramic electronic component with low equivalent series resistance as described above cannot be achieved, and a reduction in shock resistance may occur.

[0061] Furthermore, if the content of conductive carbon 32c exceeds 5.0 wt%, during the formation of the plating layer in the upper part of the first conductive resin layer 132a and the second conductive resin layer 132b, unplated defects or reduced fixation strength may occur.

[0062] Specifically, if the content of conductive carbon 32c exceeds 5.0 wt%, the viscosity ratio becomes higher due to resin shortage inside the first conductive resin layer 132a and the second conductive resin layer 132b. Therefore, when the paste used to form the conductive resin layer is applied to the outside of the body, the corners of the body become thinner, thus reducing moisture resistance and potentially leading to reliability issues.

[0063] Based on 100 parts by weight of conductive metal 32a, the content of tin (Sn) (metal 32b having a melting point lower than that of conductive metal 32a) is 10 to 50 parts by weight, thereby improving the interfacial adhesion between electrode layers 131a and 131b and conductive resin layers 132a and 132b, thus improving flexural strength.

[0064] Based on 100 parts by weight of conductive metal 32a, if the content of tin (Sn) (metal 32b having a melting point lower than that of conductive metal 32a) is less than 10 parts by weight, the interfacial adhesion between the electrode layer and the conductive resin layer is reduced, which may lead to problems related to bending strength.

[0065] Furthermore, based on 100 parts by weight of conductive metal 32a, if the content of tin (Sn) (metal 32b having a melting point lower than that of conductive metal 32a) is greater than 50 parts by weight, the impact resistance may be reduced due to the formation of a network between Sn particles.

[0066] Reference Figure 3 In the conductive resin layers 132a and 132b, conductive carbon 32c can be provided in the form of dispersion in the matrix resin 32d and can be adsorbed on the surface of the conductive metal 32a.

[0067] In addition, conductive carbon 32c can connect conductive metal 32a to tin (Sn) (metal 32b with a melting point lower than that of conductive metal 32a).

[0068] Since the conductive carbon 32c connects the conductive metal 32a to tin (Sn) (metal 32b with a lower melting point than the conductive metal 32a), the interfacial adhesion between the electrode layers 131a and 131b and the conductive resin layers 132a and 132b is improved due to the small amount of tin (Sn), while high conductivity is also ensured due to the conductive carbon 32c.

[0069] Furthermore, the conductive carbon 32c is provided in the form of dispersion in the matrix resin 32d, thus offsetting the increase in equivalent series resistance (ESR) of the multilayer ceramic electronic component caused by the matrix resin 32d.

[0070] In detail, conductive carbon 32c with excellent conductivity and low specific resistivity is dispersed in the matrix resin 32d to reduce the equivalent series resistance (ESR), thereby reducing the equivalent series resistance (ESR) of multilayer ceramic electronic components.

[0071] Furthermore, conductive carbon 32c can be graphene. When conductive carbon 32c is graphene, the graphene can be dispersed in a sheet-like manner in the conductive resin layers 132a and 132b.

[0072] Since graphene is dispersed in sheet form inside the first conductive resin layer 132a and the second conductive resin layer 132b, it has a large specific surface area, thus the effect of reducing the equivalent series resistance (ESR) of the multilayer ceramic electronic component is more excellent.

[0073] According to existing technology, in order to solve the problem of increased equivalent series resistance (ESR) of multilayer ceramic electronic components due to the conductive resin layer included in the outer electrode, attempts have been made to include carbon nanotubes (CNTs) in the conductive resin layer.

[0074] Carbon nanotubes (CNTs) are manufactured in the form of at least one of single-walled carbon nanotubes and multi-walled carbon nanotubes.

[0075] However, carbon nanotubes (CNTs) can be filled or empty columnar structures, or tubular structures containing channels. In this respect, the reduction in the equivalent series resistance (ESR) of multilayer ceramic electronic components is not significant if the content of carbon nanotubes (CNTs) is not greater than or equal to a certain amount.

[0076] In addition, carbon nanotubes (CNTs) need to be dispersed in the paste of the external electrode in order to allow intermetallic contact and tunneling in the conductive resin layer.

[0077] On the other hand, if the amount of carbon nanotubes (CNTs) is excessive in order to increase the reduction effect of the equivalent series resistance (ESR) of the multilayer ceramic electronic components, problems related to the dispersion of carbon nanotubes (CNTs) in the paste of the external electrode may occur.

[0078] Furthermore, if the carbon nanotube (CNT) content is too high, problems such as uncoated defects or reduced fixation strength may occur during the formation of the coating in the upper part of the conductive resin layer.

[0079] In addition, if the content of carbon nanotubes (CNTs) is too high, the content of matrix resin contained in the conductive resin layer is relatively low, so the impact reduction effect caused by the elasticity of the conductive resin layer cannot be obtained.

[0080] However, according to embodiments of this disclosure, the conductive carbon 32c in the first conductive resin layer 132a and the second conductive resin layer 132b includes sheet-like graphene 32c with a large specific surface area, thus the reduction effect of the equivalent series resistance (ESR) of the multilayer ceramic electronic component can be even better.

[0081] In other words, since graphene 32c according to the embodiments of the present disclosure has a sheet-like structure and a large specific surface area compared with carbon nanotubes, it is possible to achieve excellent results in reducing the equivalent series resistance (ESR) of multilayer ceramic electronic components using only a small amount of graphene.

[0082] Furthermore, since a small amount of graphene 32c has higher conductivity than carbon nanotubes, graphene can be uniformly dispersed during the fabrication of the external electrode paste, thus ensuring excellent reliability.

[0083] Furthermore, the first conductive resin layer 132a and the second conductive resin layer 132b include graphene 32c, which is a conductive carbon with a content within a certain range. Therefore, during the formation of the above coatings, there will be no problem of uncoated defects or reduced fixation strength.

[0084] Furthermore, even when the first conductive resin layer 132a and the second conductive resin layer 132b include a small amount of graphene 32c, a reduction in the equivalent series resistance (ESR) of the multilayer ceramic electronic component can be achieved. Therefore, the content of the matrix resin can be included in a manner similar to that of the prior art. Consequently, an impact mitigation effect due to the elasticity of the conductive resin layer can be obtained in a manner similar to that of the prior art.

[0085] Furthermore, as described above, the first conductive resin layer 132a and the second conductive resin layer 132b include a conductive metal 32a and tin (Sn) (a metal 32b having a melting point lower than that of the conductive metal 32a), and conductive carbon 32c connects the conductive metal 32a and tin (Sn) 32b, thereby improving the bending strength of the multilayer ceramic capacitor and achieving high conductivity.

[0086] As a conductive carbon, graphene 32c has a major axis length of 0.2 nm to 10 μm and a minor axis length of 0.2 nm to 10 μm, but it is not necessarily limited to these lengths.

[0087] According to embodiments of this disclosure, graphene 32c can be disposed in such a way that at least one piece of graphene is disposed in an area of ​​1μm × 1μm (width × height) in the first conductive resin layer 132a and the second conductive resin layer 132b. For example, the amount of graphene 32c can be disposed in the first conductive resin layer 132a and the second conductive resin layer 132b at a sufficient concentration, such that at least one piece of graphene is disposed in an area of ​​1μm × 1μm (width × height) in the cross-section of the first conductive resin layer 132a and the second conductive resin layer 132b.

[0088] There are no particular limitations on the measurement of graphene 32c, and for example, graphene can be measured in an area of ​​1 μm × 1 μm (width × height) in the first conductive resin layer 132a and the second conductive resin layer 132b.

[0089] For example, the measurement of graphene 32c in an area of ​​1 μm × 1 μm (width × height) in the first conductive resin layer 132a and the second conductive resin layer 132b was performed in an image obtained by scanning a cross section in the length-thickness direction of the multilayer ceramic capacitor using a transmission electron microscope (TEM).

[0090] In detail, graphene 32c was measured in an area of ​​1 μm × 1 μm (width × height) for the region of the first conductive resin layer 132a and the second conductive resin layer 132b obtained from an image (a cross section in the length-thickness (LT) direction cut at the center of the width (W) direction of the multilayer ceramic capacitor using transmission electron microscopy (TEM) scanning).

[0091] Figure 4 This is a schematic enlarged view showing graphene as can be used in one construction of this disclosure.

[0092] Reference Figure 4 Graphene 32c can be in the form of multiple stacked sheet-like structures.

[0093] Because of the large specific surface area of ​​each sheet structure, the reduction in equivalent series resistance (ESR) of multilayer ceramic electronic components can be excellent even with only a small amount of graphene 32c in the form of multiple sheet structures stacked together.

[0094] In other words, graphene 32c, which has low specific resistance and excellent conductivity, has sheet-like structures with large specific surface areas, and these sheet-like structures are stacked into multiple sheet-like structures. Therefore, by using only a small amount of graphene, the reduction in equivalent series resistance (ESR) of multilayer ceramic electronic components can be excellent.

[0095] Furthermore, even when the first conductive resin layer 132a and the second conductive resin layer 132b include a small amount of graphene 32c, a reduction in the equivalent series resistance (ESR) of the multilayer ceramic electronic component can be achieved. Therefore, the content of the matrix resin can be included in a manner similar to that of the prior art. Consequently, an impact mitigation effect due to the elasticity of the conductive resin layer can be obtained in a manner similar to that of the prior art.

[0096] Furthermore, the first conductive resin layer 132a and the second conductive resin layer 132b include a conductive metal 32a and a metal 32b, such as tin (Sn), having a lower melting point than the conductive metal 32a, and conductive carbon 32c connects the conductive metal 32a and the tin (Sn) 32b, thereby improving the bending strength of the multilayer ceramic capacitor and achieving high conductivity.

[0097] The conductive metal 32a may be one or more selected from the group consisting of copper (Cu), nickel (Ni), silver (Ag), and silver-palladium (Ag-Pd), but is not limited thereto.

[0098] There are no particular restrictions on the raw materials of dielectric layer 111, as long as sufficient capacitance can be obtained. For example, the raw material of dielectric layer 111 can be barium titanate (BaTiO3) powder particles. In addition, according to the purposes of this disclosure, the material of dielectric layer 111 can be prepared by adding various ceramic additives, organic solvents, plasticizers, binders, dispersants, etc. to powder particles such as barium titanate (BaTiO3) powder particles.

[0099] Here, there are no particular limitations on the materials used to form the first internal electrode 121 and the second internal electrode 122. For example, the first internal electrode 121 and the second internal electrode 122 may include at least one of silver (Ag), lead (Pb), platinum (Pt), nickel (Ni) and copper (Cu).

[0100] The first electrode layer 131a is directly connected to the first inner electrode 121 to ensure electrical conduction between the first outer electrode 130a and the first inner electrode 121. The second electrode layer 131b is directly connected to the second inner electrode 122 to ensure electrical conduction between the second outer electrode 130b and the second inner electrode 122.

[0101] The first electrode layer 131a and the second electrode layer 131b may include a conductive metal, which may be nickel (Ni), copper (Cu), palladium (Pd), gold (Au) or an alloy thereof, but the embodiments disclosed herein are not limited thereto.

[0102] The first electrode layer 131a and the second electrode layer 131b can be sintered electrodes formed by sintering a paste containing conductive metal.

[0103] like Figure 7 As described in the embodiments, plating layers 140a and 140b may be formed on the first conductive resin layer 132a and the second conductive resin layer 132b, respectively. Plating layer 140a may include a nickel plating layer 141a and a tin plating layer 142a. Similarly, plating layer 140b may include a nickel plating layer 141b and a tin plating layer 142b. Nickel plating layers 141a and 141b are respectively disposed on the first conductive resin layer 132a and the second conductive resin layer 132b, while tin plating layers 142a and 142b may be respectively disposed on nickel plating layers 141a and 141b.

[0104] Table 1 below shows the contents of conductive metal 32a and metal 32b (having a melting point lower than that of conductive metal 32a) contained in the first conductive resin layer 132a and the second conductive resin layer 132b of the multilayer ceramic capacitor, the results of the initial equivalent series resistance (ESR) measurement and the results of the crack occurrence rate measurement during the evaluation of bending strength when the content of conductive carbon 32c is changed.

[0105] Conductive metal 32a is copper (Cu), metal 32b (which has a lower melting point than conductive metal 32a) is tin (Sn), and conductive carbon 32c is graphene.

[0106] In Table 1, when the copper (Cu):tin (Sn) content ratio is 9:1, the case where the graphene content is 0 wt% corresponds to Comparative Example 1 since conductive carbon is not included. Furthermore, based on the weight of the conductive metal, Example 1 contains 0.1 wt% graphene 32c, Example 2 contains 1.0 wt% graphene 32c, and Example 3 contains 5.0 wt% graphene 32c.

[0107] Next, the case where the copper (Cu):tin (Sn) content ratio is 5:5 (as a case where the content of a metal with a melting point lower than that of a conductive metal is 100 parts by weight based on 100 parts by weight of conductive metal) corresponds to Comparative Examples 2 to 5.

[0108] In Comparative Examples 2 to 5, the graphene content was 0 wt%, 0.1 wt%, 1.0 wt%, and 5.0 wt%, respectively.

[0109] The multilayer ceramic capacitors in the comparative example and each of the examples were manufactured with dimensions of 3216 (length × width of 3.2 mm × 1.6 mm), and Table 1 below shows the initial equivalent series resistance (ESR) of the multilayer ceramic capacitors and the results of crack initiation rate during the evaluation of bending strength.

[0110] Table 1

[0111]

[0112] Referring to Table 1, in Comparative Example 1 where the copper (Cu):tin (Sn) content ratio is 9:1 and the graphene content is 0 wt%, the equivalent series resistance (ESR) of the multilayer ceramic capacitor is high, which may be a problem.

[0113] Next, in the cases of Comparative Examples 2 to 5 where the copper (Cu):tin (Sn) content ratio is 5:5, the tin (Sn) content is excessive. Therefore, due to the formation of a network between the tin (Sn) particles, it can be seen that the cracking rate is high during the evaluation of bending strength.

[0114] On the other hand, in the case where the copper (Cu):tin (Sn) content ratio is 9:1, in Examples 1 to 3 with graphene contents of 0.1wt%, 1.0wt%, and 5.0wt%, respectively, the equivalent series resistance (ESR) of the multilayer ceramic capacitor is low, and no cracks appear during the evaluation of bending strength, thus demonstrating excellent reliability.

[0115] The multilayer ceramic electronic component according to embodiments of this disclosure can be manufactured as follows.

[0116] First, a slurry formed using powders such as barium titanate (BaTiO3) is coated onto a carrier film and dried to prepare multiple ceramic green sheets, thus preparing dielectric layer 111.

[0117] Regarding ceramic green sheets, ceramic powder, binder and solvent are mixed to prepare a slurry, and the slurry is manufactured into sheets with a thickness of a few μm using a doctor blade method.

[0118] Next, a conductive paste for the internal electrode, including nickel powder, is prepared.

[0119] Conductive paste for internal electrodes is applied to ceramic green sheets using screen printing to form internal electrodes. Multiple ceramic green sheets are then stacked, each with an internal electrode printed on it. Multiple ceramic green sheets without internal electrodes printed on them are stacked on the upper and lower surfaces of the stacked structure, and then sintered to manufacture a ceramic body 110. The ceramic body includes a first internal electrode 121 and a second internal electrode 122, a dielectric layer 111, and an upper and lower capping layer. The dielectric layer is formed by sintering ceramic green sheets with internal electrodes printed on them, and the capping layer is formed by sintering ceramic green sheets without internal electrodes printed on them.

[0120] The internal electrode can be formed as a first internal electrode and a second internal electrode.

[0121] A first electrode layer 131a and a second electrode layer 131b, respectively electrically connected to the first inner electrode 121 and the second inner electrode 122, can be formed on the outer surface of the ceramic body 110. The first electrode layer 131a and the second electrode layer 131b can be formed by sintering a paste comprising conductive metal and glass.

[0122] There are no particular limitations on the conductive metal, but it can be one or more selected from the group consisting of copper (Cu), silver (Ag), nickel (Ni) and their alloys, and the conductive metal is preferably copper (Cu) as described above.

[0123] There are no particular restrictions on the glass, but it can be a material with the same composition as the glass used to manufacture the external electrodes of multilayer ceramic capacitors according to the prior art.

[0124] A conductive resin composition comprising copper is coated onto the exterior of a first electrode layer 131a and a second electrode layer 131b to form a first conductive resin layer 132a and a second conductive resin layer 132b. The conductive resin composition may include powder of a conductive metal 32a comprising copper, tin (Sn) (i.e., a metal 32b having a melting point lower than that of the conductive metal 32a), and a matrix resin 32d, wherein the matrix resin may be an epoxy resin or a thermosetting resin.

[0125] According to embodiments of this disclosure, based on 100 parts by weight of conductive metal 32a, the first conductive resin layer 132a and the second conductive resin layer 132b further include 0.1 parts by weight to 5.0 parts by weight of conductive carbon 32c.

[0126] Based on 100 parts by weight of conductive metal 32a, the first conductive resin layer 132a and the second conductive resin layer 132b include 0.1 parts by weight to 5.0 parts by weight of conductive carbon 32c, thereby reducing the equivalent series resistance of the multilayer ceramic capacitor according to embodiments of the present disclosure.

[0127] Furthermore, based on 100 parts by weight of conductive metal 32a, the first conductive resin layer 132a and the second conductive resin layer 132b include 0.1 parts by weight to 5.0 parts by weight of conductive carbon 32c, thereby improving the bending strength of the multilayer ceramic capacitor according to the embodiments of the present disclosure and increasing its conductivity.

[0128] Additionally, based on 100 parts by weight of conductive metal 32a, the first conductive resin layer 132a and the second conductive resin layer 132b may include 10 to 50 parts by weight of tin (Sn) (i.e., metal 32b having a melting point lower than that of conductive metal 32a).

[0129] Based on 100 parts by weight of conductive metal 32a, the content of tin (Sn) (metal 32b having a melting point lower than that of conductive metal 32a) is 10 to 50 parts by weight, thereby improving the interfacial adhesion between electrode layers 131a and 131b and conductive resin layers 132a and 132b, thus improving flexural strength.

[0130] After forming the first conductive resin layer 132a and the second conductive resin layer 132b, the step of further forming a nickel plating layer and a tin plating layer thereon may be included.

[0131] Figure 5 This is a graph showing the nuclear magnetic resonance (NMR) analysis results of an external electrode paste including graphene according to an embodiment of the present disclosure.

[0132] Reference Figure 5 When nuclear magnetic resonance (NMR) analysis is performed on a paste comprising an external electrode including graphene according to an embodiment of the present disclosure, it can be seen that sp... 2 Peaks caused by carbon.

[0133] When analysis is performed on the external electrode of a multilayer ceramic capacitor coated with a paste including an external electrode of graphene according to embodiments of the present disclosure, the effects of sp can be detected in the same manner. 2 Peak a is caused by carbon.

[0134] Figure 6 This is a graph showing the Raman analysis results of a graphene-containing conductive resin layer according to an embodiment of the present disclosure.

[0135] Reference Figure 6According to another embodiment of the present disclosure, a multilayer ceramic electronic component 100 includes: a ceramic body 110 including a dielectric layer 111 and inner electrodes 121 and 122; electrode layers 131a and 131b respectively connected to the inner electrodes 121 and 122; and conductive resin layers 132a and 132b respectively formed on the electrode layers 131a and 131b and including a conductive metal, a metal having a melting point lower than that of the conductive metal, conductive carbon, and a matrix resin, and two peaks were detected in the Raman analysis of the conductive resin layers 132a and 132b.

[0136] like Figure 6 As shown in the Raman analysis plots, in Examples 1 to 3, two peaks were detected in the samples used as embodiments of this disclosure. In another example, the Raman analysis plot of graphite showed only one peak.

[0137] In another embodiment of this disclosure, two peaks were detected in the D band and the G band.

[0138] Furthermore, in the case of graphite, only one peak was detected in the G-band.

[0139] In another embodiment of this disclosure, conductive resin layers 132a and 132b comprise graphene as conductive carbon.

[0140] In the Raman analysis of conductive resin layers 132a and 132b, two peaks were detected because conductive resin layers 132a and 132b contain graphene, and the Raman analysis curves are different from those of other carbon materials.

[0141] As described above, in an exemplary embodiment of the present invention, the conductive resin layer of the external electrode comprises a conductive metal, a metal having a melting point lower than that of the conductive metal, conductive carbon, and a matrix resin. By adjusting the content of the metal having a melting point lower than that of the conductive metal and the content of the conductive carbon, bending strength can be improved, and a multilayer ceramic electronic component with high conductivity can be realized.

[0142] While exemplary embodiments have been shown and described above, it will be apparent to those skilled in the art that modifications and variations may be made without departing from the scope of this disclosure as defined by the appended claims.

Claims

1. A multilayer ceramic electronic component, comprising: The ceramic body includes a dielectric layer and an internal electrode; An electrode layer, comprising a first conductive metal and glass, is connected to the inner electrode; as well as A conductive resin layer is disposed on the electrode layer and includes a second conductive metal, a third conductive metal having a melting point lower than that of the second conductive metal, conductive carbon, and a matrix resin. In this configuration, a portion of the conductive carbon connects the second conductive metal and the third conductive metal to each other, and a portion of the conductive carbon connects the second conductive metal to the electrode layer.

2. The multilayer ceramic electronic component according to claim 1, wherein, The content of conductive carbon in the conductive resin layer is from 0.4 wt% to 5.0 wt% based on the weight of the conductive resin layer.

3. The multilayer ceramic electronic component according to claim 1, wherein, The third conductive metal is tin.

4. The multilayer ceramic electronic component according to claim 3, wherein, Based on 100 parts by weight of the second conductive metal, the conductive resin layer contains 10 to 50 parts by weight of tin.

5. The multilayer ceramic electronic component according to claim 1, wherein, The conductive carbon is at least one of graphene, carbon nanotubes, and carbon black.

6. The multilayer ceramic electronic component according to claim 5, wherein, The conductive carbon is graphene, and the length of the long axis of the graphene is from 0.2 nm to 10 μm.

7. The multilayer ceramic electronic component according to claim 5, wherein, The conductive carbon is graphene, and the short axis of the graphene has a length of 0.2 nm to 10 μm.

8. The multilayer ceramic electronic component according to claim 6 or 7, wherein, The graphene is arranged such that at least one piece of graphene is disposed in an area of ​​1μm×1μm in the cross-section of the conductive resin layer, wherein 1μm×1μm is the width×height.

9. A multilayer ceramic electronic component, comprising: The ceramic body includes a dielectric layer and an internal electrode; An electrode layer, comprising a first conductive metal and glass, is connected to the inner electrode; as well as A conductive resin layer is disposed on the electrode layer and includes a second conductive metal, a third conductive metal having a melting point lower than that of the second conductive metal, conductive carbon, and a matrix resin. The third conductive metal is tin. The second conductive metal in the conductive resin layer includes at least one of copper, nickel, silver, and silver-palladium. In this configuration, a portion of the conductive carbon connects the second conductive metal and the third conductive metal to each other, and a portion of the conductive carbon connects the second conductive metal to the electrode layer.

10. The multilayer ceramic electronic component according to claim 9, wherein, Based on 100 parts by weight of the second conductive metal, the conductive carbon content in the conductive resin layer is from 0.1 parts by weight to 5.0 parts by weight.

11. The multilayer ceramic electronic component according to claim 9, wherein, Based on 100 parts by weight of the second conductive metal, the conductive resin layer contains 10 to 50 parts by weight of tin.

12. The multilayer ceramic electronic component according to claim 9, wherein, The conductive carbon is at least one of graphene, carbon nanotubes, and carbon black.

13. The multilayer ceramic electronic component according to claim 12, wherein, The conductive carbon is graphene, and the length of the long axis of the graphene is from 0.2 nm to 10 μm.

14. The multilayer ceramic electronic component according to claim 12, wherein, The conductive carbon is graphene, and the short axis of the graphene has a length of 0.2 nm to 10 μm.

15. The multilayer ceramic electronic component according to claim 13 or 14, wherein, The graphene is arranged such that at least one piece of graphene is disposed in an area of ​​1μm×1μm in the cross-section of the conductive resin layer, wherein 1μm×1μm is the width×height.

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