Multilayer electronic component

Abstract

To provide a method of improving the moisture resistance reliability of a multilayer electronic component and improving the connectivity between an internal electrode and an external electrode.SOLUTION: A multilayer electronic component includes a main body 110 including a dielectric layer 111 and internal electrodes 121 and 122 disposed alternately with the dielectric layer in a first direction, external electrodes 131 and 132 disposed outside the main body, and oxide layers 141 and 142 disposed between the main body and the external electrodes and connecting the internal electrodes and the external electrodes. The oxide layer includes one or more of Ni oxide and Cu oxide. Between one surface of the main body and a terminal of the internal electrode, at least one groove part is disposed and the oxide layer is in contact with the terminal of the internal electrode inside the groove part.SELECTED DRAWING: Figure 2

Description

[Technical field]

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

[0002] Multi-layered ceramic capacitors (MLCCs), which are one type of multi-layered electronic component, are chip-type capacitors that are mounted on printed circuit boards of various electronic products such as visual devices such as liquid crystal displays (LCDs) and plasma display panels (PDPs), computers, smartphones, and mobile phones, and serve to charge and discharge electricity.

[0003] Such multilayer ceramic capacitors have advantages of being small, having high capacitance, and being easy to mount, and can be used as components of various electronic devices. In particular, as various electronic devices such as computers and mobile devices are becoming smaller and have higher output, there is an increasing demand for multilayer ceramic capacitors to be smaller and have higher capacitance.

[0004] However, as multilayer ceramic capacitors have become smaller and have higher capacitance, their dielectric layers and internal electrodes have become thinner and more susceptible to deterioration due to changes in the external environment, which can cause problems such as reduced moisture resistance reliability of the multilayer ceramic capacitor due to the penetration of moisture from the outside.

[0005] In addition, in order to make the internal electrodes thinner, it is generally necessary to use finer metal powder than conventional ones, but when finer metal powder is used, the shrinkage start temperature of the internal electrodes is shifted to a lower temperature, which may cause a difference in shrinkage behavior between the internal electrodes and the dielectric layers. In this case, the shrinkage rate of the internal electrodes is higher than that of the dielectric layers, which may cause a problem of reduced connectivity between the internal electrodes and the external electrodes.

[0006] Therefore, there is a need to study a structure of a multilayer ceramic capacitor that can improve the moisture resistance reliability and the connectivity between the internal electrodes and the external electrodes. Summary of the Invention [Problem to be solved by the invention]

[0007] One of the various objects of the present invention is to improve the moisture resistance reliability of multilayer electronic components.

[0008] One of the various objects of the present invention is to improve connectivity between the internal and external electrodes.

[0009] However, the object of the present invention is not limited to the above-mentioned contents, and can be more easily understood in the course of describing specific embodiments of the present invention. [Means for solving the problem]

[0010] One embodiment of the present invention provides a multilayer electronic component including a body including dielectric layers and internal electrodes alternately arranged with the dielectric layers in a first direction, external electrodes arranged on the outside of the body, and an oxide layer arranged between the body and the external electrodes and connecting the internal electrodes and the external electrodes, the oxide layer including at least one of Ni oxide and Cu oxide.

[0011] One embodiment of the present invention provides a multilayer electronic component including a body including dielectric layers and internal electrodes arranged alternately with the dielectric layers, an oxide layer including a metal oxide and in contact with one side of the body, and an external electrode arranged on the oxide layer, wherein at least one groove is arranged between the one side of the body and an end of the internal electrode, and the oxide layer is in contact with the end of the internal electrode inside the groove. Effect of the Invention

[0012] One of the various effects of the present invention is that it can improve the moisture resistance reliability of a multilayer electronic component.

[0013] One of the advantages of the present invention is that it can improve the connectivity between the internal electrodes and the external electrodes. [Brief description of the drawings]

[0014] [Figure 1] 1 is a perspective view showing a schematic configuration of a multilayer electronic component according to an embodiment of the present invention; [Diagram 2] FIG. 2 is a cross-sectional view showing a schematic cross section taken along line II' of FIG. [Diagram 3] FIG. 2 is a cross-sectional view showing a schematic cross section taken along line II-II' of FIG. [Figure 4] FIG. 3 is a cross-sectional view showing part of the main body of FIG. 2, and is shown roughly for explaining the detailed configuration of the main body. [Diagram 5] FIG. 3 is an enlarged view of a K1 region in FIG. [Figure 6] FIG. 3 is an enlarged view of region K2 in FIG. 2. [Figure 7] FIG. 6 is an enlarged view of region K3 in FIG. 5. [Figure 8] 1 is a graph that roughly shows X-ray diffraction patterns for oxide layers of an embodiment and a comparative example. [Figure 9] FIG. 3 is a cross-sectional view showing a schematic configuration of a multilayer electronic component according to another embodiment of the present invention, which is a modification of FIG. 2. [Figure 10] FIG. 3 is a cross-sectional view showing a schematic configuration of a multilayer electronic component according to another embodiment of the present invention, which is a modification of FIG. 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Hereinafter, the 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. Furthermore, the embodiments of the present invention are provided to more completely explain the present invention to ordinary skilled artisans. Therefore, the shapes and sizes of elements in the drawings may be enlarged or reduced (or highlighted or simplified) for clearer explanation, and elements indicated by the same reference numerals in the drawings are the same elements.

[0016] In order to clearly explain the present invention in the drawings, parts that are not relevant to the explanation are omitted, and the size and thickness of each component shown in the drawings are arbitrarily shown for convenience of explanation, so the present invention is not necessarily limited to those shown in the drawings. Also, components having the same function within the same concept will be described using the same reference numerals. Furthermore, throughout the specification, when a part "includes" a certain component, this does not mean that other components are excluded, but that the part may further include other components, unless otherwise specified to the contrary.

[0017] In the drawings, a first direction may be defined as a thickness T direction, a second direction may be defined as a length L direction, and a third direction may be defined as a width W direction.

[0018] Multilayer Electronic Components FIG. 1 is a perspective view showing a multilayer electronic component according to one embodiment of the present invention, FIG. 2 is a cross-sectional view showing the I-I' section of FIG. 1, FIG. 3 is a cross-sectional view showing the II-II' section of FIG. 1, FIG. 4 is a cross-sectional view showing a portion of the main body of FIG. 2, shown generally for explaining the detailed configuration of the main body, FIG. 5 is an enlarged view of area K1 of FIG. 2, FIG. 6 is an enlarged view of area K2 of FIG. 2, and FIG. 7 is an enlarged view of area K3 of FIG. 5.

[0019] Hereinafter, a multilayer electronic component 100 according to an embodiment of the present invention will be described in detail with reference to Figures 1 to 7. In addition, the description will be based on a multilayer ceramic capacitor (hereinafter, referred to as "MLCC"), which is an example of a multilayer electronic component, but the present invention is not limited thereto and can be applied to various multilayer electronic components, such as an inductor, a piezoelectric element, a varistor, or a thermistor.

[0020] The laminated electronic component 100 according to an embodiment of the present invention may include a body 110 including a dielectric layer 111 and internal electrodes 121 and 122 , external electrodes 131 and 132 , and oxide layers 141 and 142 .

[0021] As described above, in the past, as the dielectric layer 111 and the internal electrodes 121, 122 are thinned, there may be a problem that the moisture resistance reliability is reduced due to the penetration of moisture from the outside. In addition, when fine metal powder is used to thin the internal electrodes 121, 122, there may be a problem that the connectivity between the internal electrodes 121, 122 and the external electrodes 131, 132 is reduced due to the difference in shrinkage behavior between the internal electrodes 121, 122 and the dielectric layer 111.

[0022] Meanwhile, the multilayer electronic component 100 according to one embodiment of the present invention includes oxide layers 141, 142 disposed between the body 110 and the external electrodes 131, 132, thereby suppressing the penetration of moisture and the like from the outside and improving the connectivity between the internal electrodes 121, 122 and the external electrodes 131, 132.

[0023] Each component included in the multilayer electronic component 100 according to one embodiment of the present invention will now be described in more detail.

[0024] There is no particular limitation on the specific shape of the main body 110. As shown in the figure, the main body 110 can be formed in a hexahedron shape or a shape similar thereto. Due to the shrinkage of the ceramic powder contained in the main body 110 and the polishing of the corners during the firing process, the main body 110 may not have a hexahedron shape with perfect straight lines, but can substantially have a hexahedron shape.

[0025] The main body 110 can 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 to the fourth surface 1, 2, 3, 4 and facing each other in a third direction.

[0026] The main body 110 can include a dielectric layer 111 and internal electrodes 121, 122 alternately arranged with the dielectric layer 111. The internal electrodes 121, 122 can be alternately arranged with the dielectric layer 111 in the first direction, for example. The plurality of 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 include, for example, a dielectric material. The dielectric material can be BaTiO3, (Ba 1-x Ca x )TiO3 (0 < x < 1) in which Ca (calcium), Zr (zirconium), etc. are partially solid-solved in BaTiO3, Ba(Ti 1-y Ca y )O3 (0 < y < 1), (Ba 1-x Ca x )(Ti 1-y Zr y )O3 (0 < x < 1, 0 < y < 1), or Ba(Ti 1-y Zr y )O3 (0 < y < 1), etc., but the present invention is not limited thereto.

[0028] The average thickness td of the dielectric layer 111 does not need to be particularly limited, but may be, for example, 0.01 μm to 10 μm. The average thickness td of the dielectric layer 111 may be set arbitrarily according to the desired characteristics and applications, and for example, in the case of a small IT electronic component, the average thickness td of at least one of the multiple dielectric layers 111 may be 0.4 μm or less in order to achieve miniaturization and high capacity.

[0029] Generally, the thinner the dielectric layer 111, the more likely it is that moisture from the outside that has penetrated into the main body 110 will deteriorate the insulation resistance, resulting in a problem of reduced reliability of the multilayer electronic component. Meanwhile, in the case of the multilayer electronic component 100 according to one embodiment of the present invention, by including the oxide layers 141, 142 disposed between the main body 110 and the external electrodes 131, 132, the reliability of the multilayer electronic component 100 can be ensured even when the average thickness td of the dielectric layer 111 is 0.4 μm or less.

[0030] The internal electrodes 121, 122 are alternately arranged with the dielectric layer 111, and for example, a first internal electrode 121 and a second internal electrode 122, which are a pair of electrodes having different polarities, may be arranged to face each other with the dielectric layer 111 in between. The first internal electrode 121 and the second internal electrode 122 may be electrically isolated from each other by the dielectric layer 111 arranged therebetween.

[0031] The first internal electrode 121 may be spaced apart from the fourth surface 4 and may extend toward the third surface 3. The second internal electrode 122 may be spaced apart from the third surface 3 and may extend toward the fourth surface 4. The first internal electrode 121 may be electrically connected to the first external electrode 131 on the third surface 3 side, and the second internal electrode 122 may be electrically connected to the second external electrode 132 on the fourth surface 4 side.

[0032] The conductive metal contained in the internal electrodes 121, 122 may be one or more of Ni, Cu, Pd, Ag, Au, Pt, Sn, W, Ti, and alloys thereof, and more preferably may include Ni, but the present invention is not limited thereto.

[0033] The average thickness te of the internal electrodes 121, 122 does not need to be particularly limited, but may be, for example, 0.01 μm to 3 μm or less. The average thickness te of the internal electrodes 121, 122 may be set arbitrarily according to the desired characteristics and applications, and for example, in the case of a small IT electronic component, the average thickness te of at least one of the multiple internal electrodes 121, 122 may be 0.4 μm or less in order to achieve miniaturization and high capacity.

[0034] As described above, in the case of the multilayer electronic component 100 according to an embodiment of the present invention, by including the oxide layers 141, 142 disposed between the body 110 and the external electrodes 131, 132, the reliability of the multilayer electronic component can be ensured even when the average thickness te of the internal electrodes 121, 122 is 0.4 μm or less.

[0035] The average thickness td of the dielectric layer 111 and the average thickness te of the internal electrodes 121 and 122 refer to the size in the first direction of the dielectric layer 111 and the internal electrodes 121 and 122, respectively. The average thickness td of the dielectric layer 111 and the average thickness te of the internal electrodes 121 and 122 may be measured by scanning the cross sections of the body 110 in the first and second directions with a scanning electron microscope (SEM) with a magnification of 10,000. More specifically, the average thickness td of the dielectric layer 111 may be measured by measuring the thickness at a number of points of one dielectric layer 111, for example, 30 points equally spaced in the second direction, and then measuring the average value. In addition, the average thickness te of the internal electrodes 121 and 122 may be measured by measuring the thickness at a number of points of one internal electrode 121 and 122, for example, 30 points equally spaced in the second direction, and then measuring the average value. The 30 equally spaced points may be designated by a capacitance forming unit Ac, which will be described later. On the other hand, if such average value measurements are performed on 10 dielectric layers 111 and 10 internal electrodes 121, 122, respectively, and then the average values ​​are measured, the average thickness td of the dielectric layers 111 and the average thickness te of the internal electrodes 121, 122 can be further generalized.

[0036] The body 110 may include a capacitance forming part Ac that is disposed inside the body 110 and includes first and second internal electrodes 121, 122 that are alternately disposed with a dielectric layer 111 therebetween to form a capacitance, and a first cover part 112 and a second cover part 113 that are disposed on both sides of the capacitance forming part Ac facing each other in a first direction. The cover parts 112, 113 may basically serve to prevent damage to the internal electrodes due to physical or chemical stress. The cover parts 112, 113 may have the same configuration as the dielectric layer 111, except that they do not include internal electrodes.

[0037] The thickness of the cover parts 112, 113 is not particularly limited. However, in order to reduce the size and increase the capacity of the multilayer electronic component, the average thickness tc of the cover parts 112, 113 may be 20 μm or less. As described above, in the case of the multilayer electronic component 100 according to an embodiment of the present invention, the reliability of the multilayer electronic component 100 can be ensured even when the average thickness tc of the cover parts 112, 113 is 20 μm or less by including the oxide layers 141, 142 disposed between the body 110 and the external electrodes 131, 132. Here, the average thickness of the cover parts 112, 113 means the average thickness of each of the first cover part 112 and the second cover part 113.

[0038] The average thickness tc of the cover parts 112, 113 may mean the average size of the cover parts 112, 113 in the first direction, and may be the average value of the first direction size measured at five equally spaced points in the first and second direction cross sections of the body 110.

[0039] The body 110 may include a first margin portion 114 and a second margin portion 115 disposed on both sides of the capacitance forming portion Ac facing each other in the third direction. That is, the margin portions 114 and 115 may refer to regions between both ends of the internal electrodes 121 and 122 and the boundary surface of the body 110 in a cross section of the body 110 cut in the first and third directions.

[0040] The margin portions 114 and 115 may include the same material as the dielectric layer 111, except that they do not include the internal electrodes 121 and 122. The margin portions 114 and 115 may essentially serve to prevent damage to the internal electrodes 121 and 122 due to physical or chemical stress.

[0041] The average thickness of the margin portions 114, 115 is not particularly limited. However, in order to reduce the size and increase the capacity of the multilayer electronic component, the average thickness of the margin portions 114, 115 may be 15 μm or less. As described above, the multilayer electronic component 100 according to an embodiment of the present invention includes the oxide layers 141, 142 disposed between the body 110 and the external electrodes 131, 132, so that the reliability of the multilayer electronic component 100 can be ensured even when the average thickness of the margin portions 114, 115 is 20 μm or less. Here, the average thickness of the margin portions 114, 115 refers to the average thickness of each of the first margin portion 114 and the second margin portion 115.

[0042] The average thickness of the margin portions 114, 115 may refer to the average size in the third direction of the margin portions 114, 115, and may be the average value of the third direction sizes measured at five equally spaced points in the first and third direction cross sections of the body 110.

[0043] Meanwhile, when a magnetic material is applied to the body 110 instead of a dielectric material, the multilayer electronic component can function as an inductor. The magnetic material can be, for example, ferrite and / or metal magnetic particles. When the multilayer electronic component functions as an inductor, the internal electrode can be a coil-type conductor.

[0044] Furthermore, the multilayer electronic component can function as a piezoelectric element when a piezoelectric material is applied instead of a dielectric material to the body 110. The piezoelectric material can be, for example, PZT (lead zirconate titanate).

[0045] In addition, when a ZnO-based or SiC-based material is applied to the body 110 instead of a dielectric material, the multilayer electronic component can function as a varistor, and when a spinel-based material is applied to the body 110 instead of a dielectric material, the multilayer electronic component can function as a thermistor.

[0046] That is, the multilayer electronic component 100 according to an embodiment of the present invention can function not only as a multilayer ceramic capacitor, but also as an inductor, a piezoelectric element, a varistor, or a thermistor by appropriately changing the material and structure of the body 110.

[0047] The external electrodes 131, 132 may be disposed outside the body 110. Specifically, the external electrodes 131, 132 may be disposed on the third surface 3 and the fourth surface 3, 4, and may extend onto parts of the first surface, the second surface, the fifth surface and the sixth surface 1, 2, 5, 6. The external electrodes 131, 132 may include a first external electrode 131 disposed on the third surface 3 and electrically connected to the first internal electrode 121, and a second external electrode 132 disposed on the fourth surface 4 and electrically connected to the second internal electrode 122.

[0048] The external electrodes 131, 132 may include electrode layers 131a, 132a disposed on the oxide layers 141, 142 and plating layers 131b, 132b disposed on the electrode layers 131a, 132a. That is, the first external electrode 131 may include a first electrode layer 131a and a first plating layer 131b disposed on the first electrode layer 131a, and the second external electrode 132 may include a second electrode layer 132a and a second plating layer 132b disposed on the second electrode layer 132a.

[0049] The electrode layers 131a and 132a may be, for example, fired electrode layers containing metal and glass. Alternatively, the electrode layers 131a and 132a may be conductive resin layers containing metal and resin. Alternatively, the electrode layers 131a and 132a may be thin film layers formed by a thin film formation method such as a sputtering method or a vapor deposition method. The electrode layers 131a and 132a are preferably fired electrode layers, but the present invention is not limited thereto, and the electrode layers 131a and 132a may include one or more of the fired electrode layers, conductive resin layers, and thin film layers.

[0050] The metal contained in the first electrode layers 131a, 132a may include Cu, Ni, Sn, Pd, Pt, Au, Ag, Pb and / or alloys containing these, and more preferably may include Cu, although the present invention is not limited thereto.

[0051] The plating layers 131b, 132b can improve mounting characteristics. The type of the plating layers 131b, 132b is not particularly limited, and may be a plating layer containing Ni, Sn, Pd and / or an alloy containing these, and may be formed of a plurality of layers. The plating layers 131b, 132b may be, for example, a Ni plating layer or a Sn plating layer, and may be in a form in which a Ni plating layer and a Sn plating layer are formed in sequence. The plating layers 131b, 132b may also include a plurality of Ni plating layers and / or a plurality of Sn plating layers.

[0052] In the drawings, the multilayer electronic component 100 is illustrated as having two external electrodes 131, 132, but this is not limited to this, and the number and shape of the external electrodes 131, 132 may vary depending on the shape of the internal electrodes 121, 122 and other purposes.

[0053] The oxide layers 141, 142 may be disposed between the body 110 and the external electrodes 131, 132, for example, and may connect the internal electrodes 121, 122 to the external electrodes 131, 132. The oxide layers 141, 142 may include a first oxide layer 141 disposed between the body 110 and the first external electrode 131, and connecting the first internal electrode 121 to the first external electrode 131, and a second oxide layer 142 disposed between the body 110 and the second external electrode 132, and connecting the second internal electrode 122 to the second external electrode 132.

[0054] The oxide layers 141, 142 may, for example, be in contact with one surface of the body 110, and the external electrodes 131, 132 may be disposed on the oxide layers 141, 142. That is, the oxide layers 141, 142 may include a first oxide layer 141 in contact with the third surface 3 of the body 110 and a second oxide layer 142 in contact with the fourth surface 4 of the body 110, and the first external electrode 131 may be disposed on the first oxide layer 141, and the second external electrode 132 may be disposed on the second oxide layer 142.

[0055] More specifically, the oxide layers 141 and 142 may include a first oxide layer 141 covering the third surface 3, and a second oxide layer 142 spaced apart from the first oxide layer 141 and covering the fourth surface 4. The first and second oxide layers 141 and 142 may be disposed between an extension line E1 of the first surface and an extension line E2 of the second surface, but the present invention is not limited thereto.

[0056] When a voltage is applied, the oxide layers 141 and 142 can electrically connect the internal electrodes 121 and 122 and the external electrodes 131 and 132 through a tunneling effect. The tunneling effect refers to a phenomenon in which electrons can move between metals in a metal-insulator-metal junction, and when a voltage of a certain magnitude or more is applied to an insulator, electrons tunnel through the insulator and move between the metals. That is, when an electric field of a certain magnitude or more is applied, electrons tunnel through the oxide layers 141 and 142 and move between the internal electrodes 121 and 122 and the external electrodes 131 and 132. The tunneling effect occurs because the oxide layers 141 and 142 are formed as thin films using a sol-gel method described below.

[0057] The oxide layers 141 and 142 may include a metal oxide. The oxide layers 141 and 142 may be formed using a sol-gel method, as described below. The type of metal oxide included in the oxide layers 141 and 142 is not particularly limited. The metal oxide may be appropriately selected in consideration of the reactivity and dispersibility of a metal precursor used in the sol-gel method, the moisture resistance and tunneling characteristics of the metal oxide, and the like. For example, the metal oxide may include one or more of Ni oxide and Cu oxide. Since the oxide layers 141 and 142 basically include a metal oxide, it is possible to prevent moisture from the outside from penetrating into the internal electrodes 121 and 122, thereby improving the moisture resistance reliability of the multilayer electronic component 100.

[0058] In addition, the oxide layers 141 and 142 may improve connectivity between the internal electrodes 121 and 122 and the external electrodes 131 and 132. Referring to FIGS. 2 and 4, the body 110 may include at least one groove G1, G2 disposed between one surface of the body 110 contacting the oxide layers 141 and 142 and an end of the internal electrodes 121 and 122. More specifically, at least one first groove G1 may be disposed between a third surface 3 contacting the first oxide layer 141 and an end of the first internal electrode 121, and at least one second groove G2 may be disposed between a fourth surface 4 contacting the second oxide layer 142 and an end of the second internal electrode 122. The grooves G1 and G2 may be formed due to a difference in shrinkage behavior between the internal electrodes 121 and 122 and the dielectric layer 111 during the firing process of the body 110. If the firing shrinkage rate of the internal electrodes 121, 122 is greater than that of the dielectric layer 111, there is a concern that the connectivity between the internal electrodes 121, 122 and the external electrodes 131, 132 may be reduced due to the grooves G1, G2.

[0059] Meanwhile, according to an embodiment of the present invention, the oxide layers 141, 142 contact the ends of the internal electrodes 121, 122 inside the grooves G1, G2, thereby improving the connectivity between the internal electrodes 121, 122 and the external electrodes 131, 132. In the process using the sol-gel method described below, a solution for forming an oxide layer, which is a mixture of a metal precursor and an organic solvent, is coated on the outer surface of the body 110, and the solution can be easily applied inside the grooves G1, G2. As a result, the connectivity between the internal electrodes 121, 122 and the external electrodes 131, 132 can be ensured without a separate polishing process during the process in which the oxide layers 141, 142 are formed after the heat treatment process.

[0060] Hereinafter, the oxide layers 141 and 142 will be described in more detail with reference to Figures 5 to 7. Although Figures 5 to 7 show the first oxide layer 141, the first oxide layer 141 and the second oxide layer 142 may have substantially the same configuration, with the only difference being that the first oxide layer 141 is disposed on the third surface 3 and the second oxide layer 142 is disposed on the fourth surface 4. Therefore, the description of the first oxide layer 141 includes the description of the second oxide layer 142.

[0061] As shown in Figures 5 and 6, the first oxide layer 141 may include a first region 141a that is continuously arranged on the third surface 3 and forms one layer, and at least one second region 141b that extends from the first region 141a into the inside of the first groove portion G1 and contacts an end of the first internal electrode 121.

[0062] 5, the second direction size L1 of the second region 141b is not particularly limited, but may be, for example, more than 0 nm and not more than 200 nm. The grooves G1 and G2 are formed due to the difference in shrinkage behavior between the dielectric layer 111 and the internal electrodes 121 and 122 during the firing process of the body 110, so that the second direction size L1 of each of the grooves G1 and G2 may be different from each other, and the second direction size L1 of the grooves G1 and G2 may be determined randomly regardless of the positions of the grooves G1 and G2 based on the first direction.

[0063] 2, the grooves G1, G2 may not be arranged on the end side of at least one of the internal electrodes 121, 122. For example, in the first and second direction cross sections cut at the center in the third direction of the main body 110, the ratio of the number of the grooves G1, G2 to the total number of the internal electrodes 121, 122 may be, for example, 30% to 70%. That is, in the first and second direction cross sections cut at the center in the third direction of the main body 110, the ratio of the number of the first grooves G1 to the total number of the first internal electrodes 121 may be 30% to 70%, and the ratio of the number of the second grooves G2 to the total number of the second internal electrodes 122 may be 30% to 70%. Meanwhile, the ratio of the number of grooves G1, G2 can also be measured by enlarging a portion of the body 110, for example the central region in the first direction, in an image taken with a scanning electron microscope (SEM) of the first and second direction cross sections cut at the center of the body 110 in the third direction, and then measuring the ratio of the number of grooves G1, G2 to the total number of internal electrodes 121, 122 present in the enlarged region.

[0064] In one embodiment, the oxide layers 141 and 142 may include spherical nanoparticles of metal oxide. For example, the oxide layers 141 and 142 may include one or more spherical nanoparticles of Ni oxide and Cu oxide. That is, as shown in FIG. 7, the first oxide layer 141 may have a morphology in which spherical nanoparticles NP of metal oxide are aggregated. Such spherical nanoparticles NP are a structural feature that appears when synthesizing a metal oxide by a sol-gel method. Since the oxide layers 141 and 142 have a morphology in which spherical nanoparticles NP of metal oxide are aggregated, it may be advantageous for thinning the oxide layers 141 and 142, and the penetration of moisture from the outside may be effectively suppressed.

[0065] The average diameter of the spherical nanoparticles NP may be, for example, 4 nm to 20 nm, and more preferably 5 nm to 10 nm. When the average diameter of the spherical nanoparticles NP is within the above range, the oxide layers 141, 142 can be made thinner and the effect of suppressing the penetration of moisture from the outside can be more remarkable.

[0066] The average diameter of the spherical nanoparticles NP can, for example, mean the average value of the diameters of the spherical nanoparticles obtained by analyzing an image obtained by magnifying 50,000 times in the first and second direction cross-sections of the oxide layers 141 and 142 cut at the center in the third direction of the main body 110 with a scanning electron microscope (SEM) using an image analysis program, for example, the Zootos Program of Zootos Co., Ltd.

[0067] In one embodiment, the oxide layers 141 and 142 contain Ni oxide, and in the X-ray diffraction pattern for the oxide layers 141 and 142, when the intensity of the diffraction peak for the (111) crystal plane is I1 and the intensity of the diffraction peak for the (200) crystal plane is I2, I1 > I2 can be satisfied. More specifically, the oxide layers 141 and 142 can be preferentially oriented in the (111) crystal plane. Although the above I1 and I2 can vary depending on the heat treatment temperature, heat treatment time, etc., when forming the oxide layers 141 and 142 by the sol-gel method, by heat treating at a temperature of 200°C to 500°C for approximately 1 hour, I1 > I2 can be satisfied.

[0068] FIG. 8 is a graph schematically showing the X-ray diffraction patterns for the oxide layers of the embodiment and the comparative example. More specifically, the embodiment shows the X-ray diffraction pattern for Ni oxide formed by the sol-gel method according to one embodiment of the present invention, and the comparative example shows the X-ray diffraction pattern for Ni oxide formed by heat treating metallic Ni at a temperature of 100°C to 300°C. Referring to FIG. 8, it can be confirmed that one embodiment of the present invention satisfies I1 > I2, while the comparative example has I1 < I2.

[0069] The average thickness t0 of the oxide layers 141 and 142 does not need to be particularly limited. However, in one embodiment, the average thickness t0 of the oxide layers 141 and 142 can be 20 nm or more and 50 nm or less. If the average thickness t0 of the oxide layers 141 and 142 is less than 20 nm, the effect of improving the moisture resistance reliability of the present invention may be small. Furthermore, if the average thickness t0 of the oxide layers 141 and 142 exceeds 50 nm, the ESR of the multilayer electronic component 100 may be excessively increased. On the other hand, the average thickness t0 of the oxide layers 141 and 142 may be 20 nm or more. However, if the average thickness t0 of the oxide layers 141 and 142 is less than 30 nm, the oxide layer forming solution may not be uniformly applied to the third surface 3 and the fourth surface 4 of the main body 110 during the formation of the oxide layers 141 and 142, and the thickness uniformity of the oxide layers 141 and 142 may be reduced. Therefore, it is more preferable that the average thickness t0 of the oxide layers 141 and 142 is 30 nm or more and 50 nm or less.

[0070] The average thickness to of the oxide layers 141, 142 may mean the average size of the oxide layers 141, 142 in the second direction, and may be an average value of the second direction sizes measured at five equally spaced points in the first direction in a first and second direction cross section of the oxide layers 141, 142 cut at the center in the third direction of the body 110. Here, the thickness of the oxide layers 141, 142 may mean the distance in the second direction between an inner surface of the oxide layers 141, 142 in contact with one side of the body 110 and an outer surface of the oxide layers 141, 142 in contact with the external electrodes 131, 132.

[0071] 5 and 6, in an embodiment, when the thickness of the oxide layer 141 measured in the center region in the first direction of the body 110 is t1 and the thickness of the oxide layer measured in the internal electrode 121 arranged at the outermost edge in the first direction among the internal electrodes is t2, t2 / t1 may be 0.9 to 1.0. That is, the oxide layer 141 may have a uniform thickness in the first direction, thereby ensuring moisture resistance reliability without excessively increasing the ESR of the multilayer electronic component 100. The t1 and t2 may mean the size in the second direction of the oxide layers 141 and 142, and may be measured from images of the first and second direction cross sections of the oxide layers 141 and 142 cut at the center in the third direction of the body 110, photographed by a scanning electron microscope (SEM).

[0072] Figures 9 and 10 are cross-sectional views that show a schematic diagram of a multilayer electronic component according to another embodiment of the present invention, which is a modification of Figure 2. Hereinafter, the other embodiment of the present invention will be described with reference to Figures 9 and 10. However, descriptions that overlap with the embodiment of the present invention described above will be omitted.

[0073] 9, the first oxide layer 141' may cover a portion of the third surface 3, and the second oxide layer 142' may cover a portion of the fourth surface 4. Thus, the first and second oxide layers 141', 142' may be disposed between an extension line E1 of the first surface and an extension line E2 of the second surface.

[0074] In this case, the efficiency of the process can be improved by controlling the coating amount of the solution used in the sol-gel method while ensuring the effect of improving the connectivity between the internal electrodes 121 and 122 and the external electrodes 131 and 132.

[0075] Referring to FIG. 10 , a first oxide layer 141″ covers the third surface 3, and a second oxide layer 142″ covers the fourth surface 4, and the first and second oxide layers 141″, 142″ may be disposed extending over portions of the first and second surfaces 1, 2.

[0076] In this case, by covering a part of the first surface and the second surfaces 1 and 2 with the oxide layers 141'' and 142'', the effect of improving the moisture resistance reliability can be made more remarkable.

[0077] Hereinafter, an example of the manufacturing method of the multilayer electronic component 100 described above will be described.

[0078] First, ceramic powder for forming the dielectric layer 111 is prepared. The ceramic powder is not particularly limited as long as a sufficient capacitance can be obtained. For example, a barium titanate-based material, a lead composite perovskite-based material, or a strontium titanate-based material can be used. As an example of the above ceramic powder, BaTiO3, (Ba 1-x Ca x )TiO3 (0 < x < 1) in which Ca (calcium), Zr (zirconium), etc. are partially solid-solved in BaTiO3, Ba(Ti 1-y Ca y )O3 (0 < y < 1), (Ba 1-x Ca x )(Ti 1-y Zr y )O3 (0 < x < 1, 0 < y < 1), or Ba(Ti 1-y Zr y )O3 (0 < y < 1), etc. can be mentioned. Among the above ceramic powders, BaTiO3 can be synthesized, for example, by reacting a titanium raw material such as titanium dioxide and a barium raw material such as barium carbonate. Examples of the synthesis method of the above ceramic powder include a solid phase method, a sol-gel method, a hydrothermal synthesis method, etc., but the present invention is not limited thereto.

[0079] Next, after drying and pulverizing the prepared ceramic powder, an organic solvent such as ethanol and a binder such as polyvinyl butyral can be mixed to produce a ceramic slurry, and the ceramic slurry can be applied and dried on a carrier film to provide a ceramic green sheet.

[0080] Next, a conductive paste for internal electrodes containing metal powder, binder, etc. is printed on the ceramic green sheet to a predetermined thickness by screen printing or gravure printing, etc., to form an internal electrode pattern.

[0081] Thereafter, the ceramic green sheets on which the internal electrode patterns are printed are peeled off from the carrier film, and a predetermined number of ceramic green sheets on which the internal electrode patterns are printed are stacked to form a laminate, and the laminate is cut to have a predetermined chip size. Meanwhile, a predetermined number of ceramic green sheets on which the internal electrode patterns are not printed can be stacked on the upper and lower parts of the laminate in the first direction to form the cover parts 112 and 113 after firing. Also, in order to form the margin parts 114 and 115 after firing, a conductive paste for the internal electrodes can be applied on the ceramic green sheets except for the places where the margin parts 114 and 115 are to be formed, or a separate ceramic green sheet can be stacked on the cross section of the cut chip in the third direction.

[0082] The binder contained in the cut chips may be preferably removed through a debinding process. The conditions of the debinding process may vary depending on the type of binder used, and are not particularly limited. For example, the debinding process may be performed at 180° C. to 450° C. for 0.5 hours to 24 hours.

[0083] Thereafter, the debindered chip may be fired at a temperature of 1100° C. to 1300° C. to form the body 110 including the dielectric layer 111 and the internal electrodes 121 and 122. During the firing process, grooves G1 and G2 may be formed due to the difference in firing shrinkage rate between the internal electrodes 121 and 122 and the dielectric layer 111.

[0084] Next, the oxide layers 141 and 142 are formed by a sol-gel method. First, a metal precursor and an organic solvent such as methanol are mixed to prepare a solution for forming the oxide layer. The type of the metal precursor is not particularly limited and can be changed depending on the type of the target metal oxide. For example, when the metal oxide contained in the oxide layers 141 and 142 includes Ni oxide, the metal precursor can include nickel acetate tetrahydrate ((Ni(CH3CO2)2·4H2O). For example, when the metal oxide contained in the oxide layers 141 and 142 includes Cu oxide, the metal precursor can be copper acetate monohydrate (Cu(CH3COO)2·H2O), but the present invention is not limited thereto.

[0085] The content of the metal precursor may be 1 wt % to 30 wt % based on 100 wt % of the oxide layer forming solution, but the present invention is not limited thereto.

[0086] The oxide layer forming solution may be applied to the third and fourth surfaces 3 and 4 of the body 110 using a method such as spin coating or spray coating, and then dried. At this time, the oxide layer forming solution may also be applied to the grooves G1 and G2. Next, a heat treatment is performed at a temperature of 200° C. to 500° C. for about 1 hour to induce an oxidation reaction, thereby forming oxide layers 141 and 142 containing metal oxide.

[0087] Next, the external electrodes 131 and 132 are formed. When the electrode layers 131a and 132a are fired electrode layers, the electrode layers 131a and 132a can be formed by dipping the third and fourth surfaces 3 and 4 of the body 110 in a conductive paste containing metal powder and glass, and then firing the paste. At this time, the firing temperature can be, for example, 700°C to 900°C.

[0088] When the electrode layers 131a and 132a are conductive resin layers, the electrode layers 131a and 132a can be formed by applying a conductive resin composition containing metal powder and a thermosetting resin such as an epoxy resin onto the main body 110, drying the composition, and then performing a curing heat treatment at a temperature of 250° C. to 550° C. When the electrode layers 131a and 132a are thin film layers, the electrode layers 131a and 132a can be formed by using a sputtering method, a deposition method, or the like.

[0089] The method for forming the plating layers 131b and 132b is not particularly limited, and for example, electrolytic plating and / or electroless plating can be used.

[0090] However, the above-mentioned manufacturing method is just one example, and the manufacturing method of the multilayer electronic component 100 is not limited to the above-mentioned manufacturing method.

[0091] (Experimental Example) First, BaTiO3 powder, an organic solvent such as ethanol, and a binder such as polyvinyl butyral were mixed to prepare a ceramic slurry, and the ceramic slurry was then coated on a carrier film and dried to prepare a ceramic green sheet.

[0092] Next, a conductive paste for internal electrodes containing Ni powder, a binder, etc. was printed on the ceramic green sheets to a predetermined thickness to form internal electrode patterns, and the ceramic green sheets on which the internal electrode patterns were formed were stacked and cut.

[0093] Next, a binder removal process and a firing process were performed to form the body 110, and then a solution for forming an oxide layer, which was a mixture of nickel acetate tetrahydrate (Ni(CH3CO2)2·4H2O) and methanol, was spray-coated onto the body 110 and then dried. Next, the body 110 was heat-treated at a temperature of 400°C for about 1 hour to form oxide layers 141 and 142 containing Ni oxide.

[0094] Next, the body 110 was dipped in a conductive paste containing Cu powder and glass, and then fired to form electrode layers 131a and 132a, and an experimental example was prepared by forming plating layers 131b and 132b in which a Ni plating layer and a Sn plating layer were sequentially formed on the electrode layers.

[0095] At this time, the average thickness of the oxide layers 141 and 142 was adjusted by adjusting the weight of the metal precursor nickel acetate tetrahydrate (Ni(CH3CO2)2·4H2O) relative to 100 wt% of the oxide layer forming solution for each sample number in Table 1 below. As the weight of nickel acetate tetrahydrate (Ni(CH3CO2)2·4H2O) increased relative to 100 wt% of the oxide layer forming solution, the average thickness of the oxide layers 141 and 142 increased.

[0096] Thereafter, a voltage of 1 V at a frequency of 1 kHz was applied to 30 sample chips for each sample number, and the average ESR value measured was shown in Table 1 below. In addition, to evaluate the moisture resistance reliability, a voltage of 1.5 Vr was applied to 400 sample chips for each sample number for 12 hours in an environment of a temperature of 85°C and a relative humidity of 85%, and if any sample showed burnt and insulation resistance was measured at 0 Ω, it was judged as defective (×), and if none showed burnt, it was judged as normal (○), and these are shown in Table 1 below.

[0097] [Table 1]

[0098] Referring to Table 1, it can be seen that the average thickness of the oxide layer exceeds 50 nm in sample 6, and the ESR increases sharply. Also, it can be seen that the ESR is good in sample 1, but the moisture resistance reliability is poor.

[0099] On the other hand, it can be confirmed that samples 2 to 5 have an average oxide layer thickness of 20 nm to 50 nm and are excellent in both ESR and moisture resistance reliability.

[0100] The present invention is not limited by the above-described embodiments and the accompanying drawings, but is limited by the scope of the accompanying claims. Therefore, various substitutions, modifications and changes can be made by a person having ordinary skill in the art within the scope of the technical idea of ​​the present invention described in the claims, and these also belong to the scope of the present invention.

[0101] In addition, the expression "one embodiment" does not mean the same embodiment, but is provided to emphasize and describe unique features that are different from each other. However, the above-described one embodiment does not exclude being realized in combination with features of another embodiment. For example, even if a matter described in a specific embodiment is not described in another embodiment, it can be understood as being related to the other embodiment, unless there is a description that contradicts or contradicts the matter in the other embodiment.

[0102] In addition, the terms "first", "second", etc. are used to distinguish one component from another and do not limit the order and / or importance of the components. In some cases, without departing from the scope of the rights, the first component may be named the second component, and similarly, the second component may be named the first component. [Explanation of symbols]

[0103] 100: Multilayer electronic components 111: Dielectric layer 112, 113: Cover part 114, 115: Margin 121, 122: Internal electrode 131, 132: External electrode 131a, 132a: Electrode layer 131b, 132b: plating layer 141, 142: oxide layer 141a: First area 141b:Second area G1, G2: Groove

Claims

1. a body including dielectric layers and internal electrodes arranged alternately with the dielectric layers in a first direction; an external electrode disposed outside the body; an oxide layer disposed between the body and the external electrode and connecting the internal electrode and the external electrode; The oxide layer includes at least one of Ni oxide and Cu oxide.

2. The multilayer electronic component according to claim 1 , wherein the oxide layer contains spherical nanoparticles of at least one of Ni oxide and Cu oxide.

3. 3. The multilayer electronic component according to claim 2, wherein the spherical nanoparticles have an average diameter of 4 nm to 20 nm.

4. the oxide layer includes Ni oxide; In the X-ray diffraction pattern for the oxide layer, the intensity of the diffraction peak for the (111) crystal plane is expressed as I １ , the intensity of the diffraction peak for the (200) crystal plane is I ２ When I １ >I ２ The multilayer electronic component according to claim 1 , which satisfies the above.

5. the body includes at least one groove disposed between a surface of the body in contact with the oxide layer and an end of the internal electrode; 2. The multilayer electronic component according to claim 1, wherein the oxide layer contacts an end of the internal electrode inside the groove.

6. the main body includes a first surface and a second surface facing each other in the first direction, a third surface and a fourth surface connected to the first surface and the second surface and facing each other in the second direction, and a fifth surface and a sixth surface connected to the first surface, the second surface and the fourth surface and facing each other in the third direction, 2. The multilayer electronic component according to claim 1, wherein the oxide layer includes a first oxide layer covering the third surface and a second oxide layer spaced apart from the first oxide layer and covering the fourth surface.

7. The multilayer electronic component according to claim 6 , wherein the first and second oxide layers are disposed between an extension of the first surface and an extension of the second surface.

8. The multilayer electronic component according to claim 6 , wherein the first and second oxide layers are disposed to extend over a portion of the first surface and a portion of the second surface.

9. 2. The multilayer electronic component according to claim 1, wherein the average thickness of the oxide layer is 20 nm or more and 50 nm or less.

10. 10. The multilayer electronic component according to claim 9, wherein the oxide layer has an average thickness of 30 nm or more.

11. 2. The multilayer electronic component according to claim 1, wherein t2 / t1 is 0.9 or more and 1.0 or less, where t1 is a thickness of the oxide layer measured in a central region in a first direction of the body, and t2 is a thickness of the oxide layer measured in an internal electrode that is arranged at an outermost edge of the internal electrodes based on the first direction.

12. a body including dielectric layers and internal electrodes interleaved with the dielectric layers; an oxide layer in contact with one surface of the body and including a metal oxide; an external electrode disposed on the oxide layer; At least one groove is disposed between one surface of the body and an end of the internal electrode, the oxide layer contacts an end of the internal electrode inside the groove.

13. The laminated electronic component according to claim 12 , wherein the oxide layer comprises spherical nanoparticles of a metal oxide.

14. the oxide layer includes Ni oxide; In the X-ray diffraction pattern for the oxide layer, the intensity of the diffraction peak for the (111) crystal plane is expressed as I １ , the intensity of the diffraction peak for the (200) crystal plane is I ２ When I １ >I ２ The multilayer electronic component according to claim 12 , which satisfies the above.

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