Multilayer electronic components

Abstract

To provide a multilayer electronic component that meets the target TCC characteristics and offers excellent reliability even when high voltage is applied. [Solution] The stacked electronic component includes a body containing a dielectric layer and internal electrodes, and external electrodes disposed on the body. The dielectric layer contains a plurality of dielectric crystal grains, and at least one of the plurality of dielectric crystal grains has a core-double shell structure including a core 11, a first shell 12 surrounding at least a part of the core, and a second shell 13 surrounding at least a part of the first shell. The first shell and the second shell contain rare earth elements, including at least one of gadolinium (Gd), yttrium (Y), dysprosium (Dy), and terbium (Tb). The average atomic percentage of rare earth elements in the first shell is higher than the average atomic percentage of rare earth elements in the second shell, and the average atomic percentage of rare earth elements in the first shell is 4.0 at% or more and 6.0 at% or less.

Description

[Technical Field]

[0001] This invention relates to a stacked electronic component. [Background technology]

[0002] A multilayer ceramic capacitor (MLCC), a type of multilayer electronic component, is a chip-type capacitor that is mounted on the printed circuit boards of various electronic products such as liquid crystal displays (LCDs), plasma display panels (PDPs), computers, smartphones, and mobile phones, and plays the role of charging or discharging electricity.

[0003] Such multilayer ceramic capacitors can be used as components in various electronic devices due to their advantages of being small, yet guaranteeing high capacitance, and being easy to implement. As various electronic devices such as computers and mobile devices become smaller and more powerful, the demand for smaller and higher-capacitance multilayer ceramic capacitors is increasing.

[0004] In particular, with the development of the automotive electronics industry, MLCCs for automotive electronics need to be able to operate smoothly even under extreme high-voltage conditions, requiring high reliability. MLCC reliability refers to the phenomenon where the capacitor's characteristics remain unchanged when a specific voltage is applied. However, MLCC reliability is affected by various factors, and its changes are particularly evident depending on the dielectric composition. Current MLCC dielectric layers are based on materials that primarily consist of a barium titanate (BaTiO3) matrix, containing fixed valence acceptor elements, rare earth elements acting as donors, variable valence acceptor elements, and further additives such as sintering aids. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2010-024126 [Overview of the project] [Problems that the invention aims to solve]

[0006] One of the various problems that this invention aims to solve is to provide a stacked electronic component that satisfies the target TCC characteristics.

[0007] One of the various problems that this invention aims to solve is to provide a stacked electronic component that is highly reliable even when high voltage is applied.

[0008] One of the various problems that this invention aims to solve is to provide a multilayer electronic component with improved reliability.

[0009] However, the various problems that the present invention aims to solve are not limited to those described above, and can be more easily understood in the process of describing specific embodiments of the present invention. [Means for solving the problem]

[0010] A stacked electronic component according to one embodiment of the present invention includes a body containing a dielectric layer and internal electrodes, and external electrodes disposed on the body, wherein the dielectric layer contains a plurality of dielectric crystal grains, and at least one of the plurality of dielectric crystal grains has a core-double shell structure including a core, a first shell surrounding at least a part of the core, and a second shell surrounding at least a part of the first shell, wherein the first and second shells contain rare earth elements, the average atomic percentage of rare earth elements in the first shell is higher than the average atomic percentage of rare earth elements in the second shell, and the average atomic percentage of rare earth elements in the first shell can be 4.0 at% or more and 6.0 at% or less. [Effects of the Invention]

[0011] One of the various effects of the present invention is that the multilayer electronic component satisfies the TCC characteristics.

[0012] One of the various effects of the present invention is that the multilayer electronic component has excellent reliability under high voltage.

[0013] One of the various effects of the present invention is to improve the reliability of the multilayer electronic component.

[0014] However, the diverse and beneficial advantages and effects of the present invention are not limited to the above-described content, and can be more easily understood in the process of explaining the specific embodiments of the present invention.

Brief Description of the Drawings

[0015] [Figure 1] A perspective view of a multilayer electronic component according to an embodiment of the present invention is schematically shown. [Figure 2] A separated perspective view showing the laminated structure of the internal electrodes is schematically shown. [Figure 3] A cross-sectional view taken along line I-I' of FIG. 1 is schematically shown. [Figure 4] A cross-sectional view taken along line II-II' of FIG. 1 is schematically shown. [Figure 5] An enlarged view of the P region of FIG. 3 is schematically shown. [Figure 6a] A schematic diagram of a core-double shell dielectric crystal grain is schematically shown. [Figure 6b] A schematic diagram of a core-double shell dielectric crystal grain is schematically shown. [Figure 7] An image obtained by mapping the gadolinium (Gd) element by the EDS mode of a scanning transmission electron microscope (STEM) for the core-double shell dielectric crystal grains of an embodiment of the present invention. [Figure 8] A graph of the atomic percentage of gadolinium (Gd) measured by performing a line profile with respect to line LP-LP' of FIG. 7.

Best Mode for Carrying Out the Invention

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

[0017] And, in order to clearly explain the present invention in the drawings, parts not related to the explanation are omitted, and the sizes and thicknesses of each configuration shown in the drawings are arbitrarily shown for convenience of explanation, so the present invention is not necessarily limited to what is shown in the drawings. Note that components having the same function within the scope of the same idea are described using the same reference numerals. Further, throughout the specification, when a certain part says that a certain component "includes", this means that other components can be further included, rather than excluding other components, unless otherwise stated to the contrary.

[0018] In the drawings, the first direction can be defined as the stacking direction or the thickness T direction, the second direction as the length L direction, and the third direction as the width W direction. <00001​​​​​​​​Hereinafter, with reference to Figures 1 to 6b, a multilayer electronic component according to one embodiment of the present invention will be described in detail. However, although a multilayer ceramic capacitor will be described as an example of a multilayer electronic component, the present invention can also be applied to various electronic products that utilize dielectric compositions, such as inductors, piezoelectric elements, varistors, or thermistors.

[0021] A stacked electronic component 100 according to one embodiment of the present invention includes a body 110 including a dielectric layer 111 and internal electrodes 121, 122, and external electrodes 131, 132 disposed on the body 110, wherein the dielectric layer 111 includes a plurality of dielectric crystal grains 10, 20, 30, and at least one of the plurality of dielectric crystal grains 10, 20, 30 has a core-double shell structure 10 including a core 11, a first shell 12 surrounding at least a part of the core 11, and a second shell 12 surrounding at least a part of the first shell 12, wherein the first and second shells 12, 13 contain rare earth elements, the average atomic percentage of rare earth elements in the first shell 12 is higher than the average atomic percentage of rare earth elements in the second shell 13, and the average atomic percentage of rare earth elements in the first shell 12 can be 4.0 at% or more and 6.0 at% or less.

[0022] The main body 110 may have dielectric layers 111 and internal electrodes 121 and 122 stacked alternately.

[0023] More specifically, the main body 110 may include a capacitance forming section Ac which includes a first internal electrode 121 and a second internal electrode 122 disposed inside the main body 110 and arranged alternately to face each other with a dielectric layer 111 in between, thereby forming a capacitance.

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

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

[0026] 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 so that they are difficult to confirm without using a scanning electron microscope (SEM).

[0027] The raw material for forming the dielectric layer 111 is not limited as long as sufficient capacitance can be obtained. Generally, perovskite (ABO3) - based materials can be used. For example, barium titanate - based materials, lead - composite perovskite - based materials, or strontium titanate - based materials can be used. The barium titanate - based material can contain BaTiO3 - based ceramic particles. Examples of the ceramic particles include BaTiO3, (Ba 1-x Ca x )TiO3 (0 < x < 1), 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.

[0028] Furthermore, the raw materials for forming the dielectric layer 111 can include particles such as barium titanate (BaTiO3), to which various additives, organic solvents, binders, dispersants, etc., can be added according to the purpose of the present invention. For example, the additives can include rare earth elements, and the rare earth elements can include, but are not limited to, at least one of gadolinium (Gd), yttrium (Y), dysprosium (Dy), and terbium (Tb). Other additives that can include are zirconium (Zr), magnesium (Mg), manganese (Mn), silicon (Si), etc.

[0029] As a result, the multiple dielectric crystal grains 10, 20, and 30, including dielectric crystal grains 10 with a core-double shell structure, dielectric crystal grains 20 with a core-shell structure, and dielectric crystal grains 30 without a core-shell structure, can contain barium (Ba) and titanium (Ti) contained in the barium titanate-based material, which is the main component raw material, and at least one of the rare earth elements, zirconium (Zr), magnesium (Mg), manganese (Mn), and silicon (Si), which are raw materials for additives.

[0030] On the other hand, since the dielectric layer 111 can be formed using a dielectric material such as barium titanate (BaTiO3), it can include a dielectric microstructure after firing. The dielectric microstructure includes multiple dielectric crystal grains, dielectric crystal grain boundaries arranged between adjacent dielectric crystal grains, and triple points arranged at points where three or more dielectric crystal grain boundaries meet, and multiple such microstructures may be included.

[0031] Here, at least one of the plurality of dielectric crystal grains may have a core-double shell structure 10 including a core 11, a first shell 12 surrounding at least a portion of the core 11, and a second shell 13 surrounding at least a portion of the first shell 12, and at least one of the plurality of dielectric crystal grains may have a core-shell structure 20 including a core 21 and a shell 22 surrounding at least a portion of the core 21. In other words, the plurality of dielectric crystal grains 10, 20, and 30 may include dielectric crystal grains 10 with a core-double shell structure, dielectric crystal grains 20 with a core-shell structure, and dielectric crystal grains 30 without a core-shell structure. More specific details will be described later.

[0032] The thickness td of the dielectric layer 111 does not need to be particularly limited.

[0033] To ensure the reliability of the multilayer electronic component 100 in a high-voltage environment, the thickness of the dielectric layer 111 may be 10.0 μm or less. Furthermore, to achieve miniaturization and high capacitance of the multilayer electronic component 100, the thickness of the dielectric layer 111 may be 3.0 μm or less, and to more easily achieve ultra-miniaturization and high capacitance, the thickness of the dielectric layer 111 may be 1.0 μm or less, preferably 0.6 μm or less, and more preferably 0.4 μm or less.

[0034] Here, the thickness td of the dielectric layer 111 can refer to the thickness td of the dielectric layer 111 that is placed between the first and second internal electrodes 121 and 122.

[0035] On the other hand, the thickness td of the dielectric layer 111 can represent the size of the dielectric layer 111 in the first direction. Furthermore, the thickness td of the dielectric layer 111 can represent the average thickness td of the dielectric layer 111, and can represent the average size of the dielectric layer 111 in the first direction.

[0036] The average size of the dielectric layer 111 in the first direction can be measured by scanning the cross-sections of the main body 110 in the first and second directions with a scanning electron microscope (SEM) at 10,000x magnification. More specifically, the average size of a single dielectric layer 111 in the first direction can be said to be the average value calculated by measuring the size of a single dielectric layer 111 in the first direction at 10 equally spaced points in the second direction in the scanned image. These 10 equally spaced points can be specified by the capacitance forming section Ac. Furthermore, by extending this measurement of average values ​​to 10 dielectric layers 111 and measuring the average values, the average size of the dielectric layer 111 in the first direction can be further generalized.

[0037] The internal electrodes 121 and 122 may be stacked alternately with the dielectric layer 111.

[0038] The internal electrodes 121 and 122 may include a first internal electrode 121 and a second internal electrode 122, and the first and second internal electrodes 121 and 122 are arranged alternately so as to face each other across the dielectric layer 111 that constitutes the main body 110, and can be exposed on the third and fourth surfaces 3 and 4 of the main body 110, respectively.

[0039] More specifically, the first internal electrode 121 can be separated from the fourth surface 4 and exposed via the third surface 3, and the second internal electrode 122 can be separated from the third surface 3 and exposed via the fourth surface 4. The first external electrode 131 is positioned on the third surface 3 of the main body 110 and connected to the first internal electrode 121, and the second external electrode 132 is positioned on the fourth surface 4 of the main body 110 and connected to the second internal electrode 122.

[0040] In other words, the first internal electrode 121 is not connected to the second external electrode 132, but can be connected to the first external electrode 131, and the second internal electrode 122 is not connected to the first external electrode 131, but can be connected to the second external electrode 132. In this case, the first and second internal electrodes 121 and 122 can be electrically isolated from each other by the dielectric layer 111 placed in between.

[0041] On the other hand, the main body 110 can be formed by alternately stacking a ceramic green sheet on which the first internal electrode 121 is printed and a second ceramic green sheet on which the second internal electrode 122 is printed, and then firing them.

[0042] The materials used to form the internal electrodes 121 and 122 are not particularly limited, and any material with excellent electrical conductivity can be used. For example, the internal electrodes 121 and 122 may include one or more of nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), gold (Au), platinum (Pt), tin (Sn), tungsten (W), titanium (Ti), and alloys thereof.

[0043] Furthermore, the internal electrodes 121 and 122 can be formed by printing a conductive paste for internal electrodes containing one or more of the following onto a ceramic green sheet: nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), gold (Au), platinum (Pt), tin (Sn), tungsten (W), titanium (Ti), and alloys thereof. While screen printing or gravure printing can be used as the printing method for the conductive paste for internal electrodes, the present invention is not limited thereto.

[0044] On the other hand, the thickness te of the internal electrodes 121 and 122 does not need to be particularly limited.

[0045] To ensure the reliability of the multilayer electronic component 100 in a high-voltage environment, the thickness te of the internal electrodes 121 and 122 may be 3.0 μm or less. Furthermore, to achieve miniaturization and high capacitance of the multilayer electronic component 100, the thickness of the internal electrodes 121 and 122 may be 1.0 μm or less, and to more easily achieve ultra-miniaturization and high capacitance, the thickness of the internal electrodes 121 and 122 may be 0.6 μm or less, and more preferably 0.4 μm or less.

[0046] Here, the thickness te of the internal electrodes 121 and 122 can mean the size of the internal electrodes 121 and 122 in the first direction. Also, the thickness te of the internal electrodes 121 and 122 means the average thickness te of the internal electrodes 121 and 122, and can mean the average size of the internal electrodes 121 and 122 in the first direction.

[0047] The average size of the internal electrodes 121 and 122 in the first direction can be measured by scanning an image of the cross-sections in the first and second directions of the main body 110 with a scanning electron microscope (SEM) at a magnification of 10,000 times. More specifically, the average size of one internal electrode in the first direction can be the average value calculated by measuring the size in the first direction at 10 equally spaced points in the second direction for one internal electrode in the scanned image. The 10 equally spaced points can be specified in the capacitance forming portion Ac. Also, when the measurement of such an average value is extended to 10 internal electrodes to measure the average value, the average size of the internal electrodes in the first direction can be further generalized.

[0048] On the other hand, in one embodiment of the present invention, the average thickness td of at least one of the plurality of dielectric layers 111 and the average thickness te of at least one of the plurality of internal electrodes 121 and 122 can satisfy 2×te < td.

[0049] In other words, the average thickness td of one dielectric layer 111 may be even greater than twice the average thickness te of one internal electrode 121 or 122. Preferably, the average thickness td of the plurality of dielectric layers 111 may be even greater than twice the average thickness te of the plurality of internal electrodes 121 and 122.

[0050] Generally, for electronic components for high-voltage electrical equipment, the main issue is the reliability problem due to the decrease in the breakdown voltage (BDV) in a high-voltage environment.

[0051] Therefore, in order to prevent a decrease in dielectric breakdown voltage under high voltage conditions, the average thickness td of the dielectric layer 111 can be made greater than twice the average thickness te of the internal electrodes 121 and 122, thereby increasing the thickness of the dielectric layer, which is the distance between the internal electrodes, and improving the dielectric breakdown voltage characteristics.

[0052] If the average thickness td of the dielectric layer 111 is less than or equal to twice the average thickness te of the internal electrodes 121 and 122, the average thickness of the dielectric layer, which is the distance between the internal electrodes, becomes thinner. This can lead to a decrease in the dielectric breakdown voltage and potentially cause a short circuit between the internal electrodes.

[0053] On the other hand, the main body 110 may include cover portions 112 and 113 that are positioned on both end surfaces (end-surfaces) of the capacity forming portion Ac in the first direction.

[0054] Specifically, it may include a first cover portion 112 positioned on one side of the volume-forming portion Ac in the first direction, and a second cover portion 113 positioned on the other side of the volume-forming portion Ac in the first direction. More specifically, it may include an upper cover portion 112 positioned on the upper part of the volume-forming portion Ac in the first direction, and a lower cover portion 113 positioned on the lower part of the volume-forming portion Ac in the first direction.

[0055] The upper cover portion 112 and the lower cover portion 113 can be formed by stacking a single dielectric layer 111 or two or more dielectric layers 111 on the upper and lower surfaces of the capacitance forming portion Ac in a first direction, and can essentially serve to prevent damage to the internal electrodes 121 and 122 due to physical or chemical stress.

[0056] The upper cover portion 112 and the lower cover portion 113 do not include the internal electrodes 121 and 122 and may contain the same material as the dielectric layer 111. That is, the upper cover portion 112 and the lower cover portion 113 may contain ceramic material, for example, barium titanate (BaTiO3) based ceramic material.

[0057] On the other hand, the thickness tc of the cover portions 112 and 113 does not need to be particularly limited.

[0058] However, in order to more easily achieve miniaturization and high capacity of stacked electronic components, the thickness tc of the cover portions 112 and 113 may be 100 μm or less, preferably 30 μm or less, and more preferably 20 μm or less for ultra-small products.

[0059] Here, the thickness tc of the cover portions 112 and 113 can mean the size of the cover portions 112 and 113 in the first direction. Furthermore, the thickness tc of the cover portions 112 and 113 can mean the average thickness tc of the cover portions 112 and 113, and can also mean the average size of the cover portions 112 and 113 in the first direction.

[0060] The average size of the cover portions 112 and 113 in the first direction can be measured by scanning the cross-sections of the main body 110 in the first and second directions with a scanning electron microscope (SEM) at 10,000x magnification. More specifically, it can mean the average value calculated by measuring the size in the first direction at 10 equally spaced points in the second direction in an image scanned from one cover portion.

[0061] Furthermore, the average size of the cover portion in the first direction measured by the method described above can be substantially the same as the average size of the cover portion in the first direction in the cross-sections (first and third directions) of the main body 110.

[0062] On the other hand, the stacked electronic component 100 may include side margin portions 114 and 115 arranged on both end surfaces (end-surfaces) of the main body 110 in the third direction.

[0063] More specifically, the side margins 114 and 115 may include a first side margin 114 located on the fifth surface 5 of the main body 110 and a second side margin 115 located on the sixth surface 6 of the main body 110.

[0064] As shown in the figure, the side margins 114 and 115 can refer to the regions between the end-surfaces of the first and second internal electrodes 121 and 122 in the third direction and the interface surface of the main body 110, with respect to the cross-sections of the main body 110 in the first and third directions.

[0065] The side margin portions 114 and 115 can be formed by applying conductive paste to the ceramic green sheet applied to the capacitance forming portion Ac, except for the areas where the side margin portions 114 and 115 are formed, to form the internal electrodes 121 and 122. In order to suppress the step caused by the internal electrodes 121 and 122, the laminated internal electrodes 121 and 122 can be cut so that they are exposed on the fifth and sixth surfaces 5 and 6 of the main body 110, and then a single dielectric layer 111 or two or more dielectric layers 111 can be laminated in the third direction on both end surfaces (end-surfaces) of the capacitance forming portion Ac in the third direction.

[0066] The side margins 114 and 115 can essentially serve to prevent damage to the internal electrodes 121 and 122 due to physical or chemical stress.

[0067] The first side margin portion 114 and the second side margin portion 115 do not include the internal electrodes 121 and 122 and may contain the same material as the dielectric layer 111. That is, the first side margin portion 114 and the second side margin portion 115 may contain a ceramic material, for example, a barium titanate (BaTiO3) based ceramic material.

[0068] On the other hand, the widths wm of the first and second side margins 114 and 115 do not need to be particularly limited.

[0069] However, in order to more easily achieve miniaturization and high capacitance of the stacked electronic component 100, the width wm of the side margin portions 114 and 115 may be 100 μm or less, preferably 30 μm or less, and more preferably 20 μm or less for ultra-small products.

[0070] Here, the width wm of the side margins 114 and 115 can represent the size of the side margins 114 and 115 in the third direction. Furthermore, the width wm of the side margins 114 and 115 can represent the average width wm of the side margins 114 and 115, and can represent the average size of the side margins 114 and 115 in the third direction.

[0071] The average size of the side margins 114 and 115 in the third direction can be measured by scanning the cross-sections of the main body 110 in the first and third directions with a scanning electron microscope (SEM) at 10,000x magnification. More specifically, it can mean the average value calculated by measuring the size in the third direction at 10 equally spaced points in the first direction in an image scanned from one side margin.

[0072] One embodiment of the present invention describes a structure in which a stacked electronic component 100 has two external electrodes 131 and 132. However, the number and shape of the external electrodes 131 and 132 can be changed according to the form of the internal electrodes 121 and 122 or other purposes.

[0073] The external electrodes 131 and 132 are positioned on the main body 110 and can be connected to the internal electrodes 121 and 122.

[0074] More specifically, the external electrodes 131 and 132 may include first and second external electrodes 131 and 132, which are arranged on the third and fourth surfaces 3 and 4 of the main body 110, respectively, and connected to first and second internal electrodes 121 and 122, respectively. That is, the first external electrode 131 can be arranged on the third surface 3 of the main body and connected to the first internal electrode 121, and the second external electrode 132 can be arranged on the fourth surface 4 of the main body and connected to the second internal electrode 122.

[0075] Furthermore, the external electrodes 131 and 132 may extend and be arranged on parts of the first and second surfaces 1 and 2 of the main body 110, or on parts of the fifth and sixth surfaces 5 and 6 of the main body 110. That is, the first external electrode 131 can be arranged on parts of the first, second, fifth, and sixth surfaces 1, 2, 5, and 6 of the main body 110, and on the third surface 3 of the main body 110, and the second external electrode 132 can be arranged on parts of the first, second, fifth, and sixth surfaces 1, 2, 5, and 6 of the main body 110, and on the third surface 3 of the main body 110.

[0076] On the other hand, the external electrodes 131 and 132 may be formed using any material that has electrical conductivity, such as metal, and the specific material may be determined by considering electrical properties, structural stability, etc., and may also have a multilayer structure.

[0077] For example, the external electrodes 131 and 132 may include an electrode layer placed on the main body 110 and a plating layer placed on the electrode layer.

[0078] To give a more specific example of the electrode layer, the electrode layer may include first electrode layers 131a, 132a which are fired electrodes containing a first conductive metal and glass, or second electrode layers 131b, 132b which are resin-based electrodes containing a second conductive metal and resin.

[0079] Here, the conductive metal contained in the first electrode layers 131a and 132a can be called the first conductive metal, and the conductive metal contained in the second electrode layers 131b and 132b can be called the second conductive metal. In this case, the first conductive metal and the second conductive metal may be the same or different from each other, and if multiple conductive metals are included, only some of them may be the same conductive metal, but this is not particularly limited.

[0080] Furthermore, the electrode layers 131a, 132a, 131b, and 132b may be in a form in which a fired electrode and a resin-based electrode are sequentially formed on the main body 110.

[0081] The electrode layers 131a, 132a, 131b, and 132b may be formed by transferring a sheet containing a conductive metal onto the main body, or by transferring a sheet containing a conductive metal onto a fired electrode.

[0082] Materials with excellent electrical conductivity can be used as the conductive metal contained in the electrode layers 131a, 132a, 131b, and 132b. For example, the conductive metal may include one or more selected from the group consisting of nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), gold (Au), platinum (Pt), tin (Sn), tungsten (W), titanium (Ti), and alloys thereof, but is not particularly limited thereto.

[0083] In one embodiment of the present invention, the electrode layers 131a, 132a, 131b, and 132b may have a two-layer structure including a first electrode layer 131a, 132a and a second electrode layer 131b, 132b, thereby allowing the external electrodes 131 and 132 to include a first electrode layer 131a, 132a comprising a first conductive metal and glass, and a second electrode layer 131b, 132b disposed on the first electrode layers 131a, 132a and comprising a second conductive metal and resin.

[0084] The first electrode layers 131a and 132a, by containing glass, serve to improve bonding with the main body 110, while the second electrode layers 131b and 132b, by containing resin, serve to improve bending strength.

[0085] The first conductive metal contained in the first electrode layers 131a and 132a is not particularly limited as long as it is a material that can be electrically connected to the internal electrodes 121 and 122 for the formation of capacitance. For example, it may include one or more selected from the group consisting of nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), gold (Au), platinum (Pt), tin (Sn), tungsten (W), titanium (Ti), and alloys thereof.

[0086] The first electrode layers 131a and 132a can be formed by applying a conductive paste, which is made by adding glass frit to first conductive metal particles, and then firing it.

[0087] The second conductive metal contained in the second electrode layers 131b and 132b can serve to electrically connect with the first electrode layers 131a and 132a.

[0088] The conductive metals contained in the second electrode layers 131b and 132b are not particularly limited as long as they are materials that can be electrically connected to the electrode layers 131a and 132a, and may include one or more selected from the group consisting of nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), gold (Au), platinum (Pt), tin (Sn), tungsten (W), titanium (Ti), and alloys thereof.

[0089] The second conductive metal contained in the second electrode layers 131b and 132b may include one or more spherical particles and flake-shaped particles. That is, the second conductive metal may consist only of flake-shaped particles, only of spherical particles, or in a mixed form of flake-shaped and spherical particles. Here, spherical particles may include forms that are not perfectly spherical, for example, forms with a ratio of the length of the long axis to the short axis (long axis / short axis) of 1.45 or less. Flake-shaped particles mean particles that are flat and elongated, and are not particularly limited, but for example, the ratio of the length of the long axis to the short axis (long axis / short axis) may be 1.95 or more. The lengths of the long axis and short axis of the spherical particles and flake-shaped particles can be measured from images obtained by scanning the cross-sections in the first and second directions, which are cut in the center of the third direction of the stacked electronic component, with a scanning electron microscope (SEM).

[0090] The resin contained in the second electrode layers 131b and 132b can serve to ensure bonding and absorb shock. The resin contained in the second electrode layers 131b and 132b is not particularly limited as long as it has bonding and shock-absorbing properties and can be mixed with the second conductive metal particles to make a paste; for example, it can include epoxy resins.

[0091] Furthermore, the second electrode layers 131b and 132b may contain a plurality of second conductive metal particles, an intermetallic compound, and a resin. By including an intermetallic compound, the electrical connectivity with the first electrode layers 131a and 132a can be further improved. The intermetallic compound can play a role in improving electrical connectivity by linking the plurality of metal particles and can also play a role in surrounding the plurality of metal particles and connecting them to one another.

[0092] In this case, the intermetallic compound may include a metal having a melting point lower than the curing temperature of the resin. That is, because the intermetallic compound includes a metal having a melting point lower than the curing temperature of the resin, the metal with a melting point lower than the curing temperature of the resin melts during the drying and curing process, forming an intermetallic compound with some of the metal particles and surrounding the metal particles. In this case, the intermetallic compound may preferably include a low-melting-point metal of 300°C or lower.

[0093] For example, it may contain Sn having a melting point of 213-220°C. During the drying and hardening process, the Sn melts, and the molten Sn moistens high-melting-point metal particles such as Ag, Ni, or Cu by capillary action, reacting with some of the Ag, Ni, or Cu metal particles to form intermetallic compounds such as Ag3Sn, Ni3Sn4, Cu6Sn5, and Cu3Sn. The Ag, Ni, or Cu that do not participate in the reaction remain in the form of metal particles.

[0094] Therefore, the plurality of second conductive metal particles may include one or more of Ag, Ni, and Cu, and the intermetallic compound may include one or more of Ag3Sn, Ni3Sn4, Cu6Sn5, and Cu3Sn.

[0095] The plating layers 131c and 132c can play a role in improving mounting characteristics.

[0096] The types of plating layers 131c and 132c are not particularly limited and may be single-layer plating layers 131c and 132c containing one or more of nickel (Ni), tin (Sn), silver (Ag), palladium (Pd), and alloys thereof, or they may be formed in multiple layers.

[0097] To give a more specific example of the plating layers 131c and 132c, the plating layers 131c and 132c may be Ni plating layers or Sn plating layers, and may be in a form in which Ni plating layers and Sn plating layers are sequentially formed on the electrode layer, or may be in a form in which Sn plating layers, Ni plating layers and Sn plating layers are sequentially formed. Furthermore, the plating layers 131c and 132c may include multiple Ni plating layers and / or multiple Sn plating layers.

[0098] There is no particular limit to the size of the stacked electronic component 100.

[0099] However, in order to achieve both miniaturization and high capacitance simultaneously, the thickness of the dielectric layer and internal electrodes must be reduced and the number of layers increased. Therefore, the effects of the present invention may become more pronounced in stacked electronic components 100 of size 3216 (length × width: 3.2 mm × 1.6 mm) or smaller, or 2012 (length × width: 2.0 mm × 1.2 mm) or smaller.

[0100] The following describes one embodiment of the present invention in more detail.

[0101] In a stacked electronic component 100 according to one embodiment of the present invention, the dielectric layer 111 includes a plurality of dielectric crystal grains 10, 20, and 30, and at least one of the plurality of dielectric crystal grains has a core-double shell structure 10 including a core 11, a first shell 12 surrounding at least a part of the core 11, and a second shell 13 surrounding at least a part of the first shell 12, and the first and second shells 12 and 13 contain rare earth elements, the average atomic percentage of rare earth elements in the first shell 12 is higher than the average atomic percentage of rare earth elements in the second shell 13, and the average atomic percentage of rare earth elements in the first shell 12 can be 4.0 at% or more and 6.0 at% or less.

[0102] The dielectric layer 111 includes a plurality of dielectric crystal grains 10, 20, and 30, and at least one of the plurality of dielectric crystal grains may have a core-double shell structure 10 including a core 11, a first shell 12 surrounding at least a portion of the core 11, and a second shell 13 surrounding at least a portion of the first shell 12. In other words, the dielectric layer 111 may include dielectric crystal grains 10 with a core-double shell structure.

[0103] In the present invention, as a more specific example of a method for measuring the elemental content of each component of a stacked electronic component 100, in the case of a destructive method, the components can be analyzed using the energy dispersive X-ray spectroscopy (EDS) mode of a scanning electron microscope (SEM), the EDS mode of a transmission electron microscope (TEM), or the EDS mode of a scanning transmission electron microscope (STEM). First, an analytical sample is prepared by thinning it using a focused ion beam (FIB) in the area to be measured. Then, the damage layer on the surface of the thinned sample is removed using xenon (Xe) or argon (Ar) ion milling, and then each component to be measured is mapped from the image obtained using SEM-EDS, TEM-EDS, or STEM-EDS, and qualitative / quantitative analysis is performed. In this case, the qualitative / quantitative analysis graphs for each component can also be expressed by converting them to the mass percentage (wt%), atomic percentage (at%), or mole percentage (mol%) of each element. At this time, the number of moles of one specific component can be converted and expressed relative to the number of moles of another specific component.

[0104] Another method involves crushing the chip to select the region to be measured, and then analyzing the components of the selected region containing dielectric microstructure using instruments such as an inductively coupled plasma spectrometer (ICP-OES) or inductively coupled plasma mass spectrometer (ICP-MS).

[0105] On the other hand, in the present invention, the atomic percentage (at%) of a specific element, for example, a first element, can mean the percentage of the number of atoms of a specific first element relative to the total number of atoms of all elements, and the atomic percentage (at%) or average atomic percentage (at%) of a first element at a specific location or region can mean the percentage or average percentage of the number of atoms of a first element relative to the total number of atoms of all elements included at that specific location or region. To give a more specific example, the atomic percentage of a rare earth element at a specific location in the first shell can mean the percentage of the number of atoms of a rare earth element relative to the total number of atoms of all elements included at that specific location in the first shell, and the average atomic percentage of a rare earth element in a first shell region can mean the average percentage of the number of atoms of a rare earth element relative to the total number of atoms of all elements included in the first shell region.

[0106] Here, core 11 can mean a region where the average atomic percentage of rare earth elements is 0 at% or more and less than 2.0 at%, first shell 12 can mean a region surrounding at least a part of core 11 where the average atomic percentage of rare earth elements is 4.0 at% or more and less than 6.0 at%, and second shell 13 can mean a region surrounding at least a part of first shell 12 where the average atomic percentage of rare earth elements is 2.0 at% or more and less than 4.0 at%.

[0107] In other words, the average atomic percentage of rare earth elements in the first shell 12 may be higher than the average atomic percentage of rare earth elements in the second shell 13, the average atomic percentage of rare earth elements in the first shell 12 may be higher than the average atomic percentage of rare earth elements in the core 11, and the average atomic percentage of rare earth elements in the second shell 13 may be higher than the average atomic percentage of rare earth elements in the core 11.

[0108] The first and second shells 12 and 13 contain rare earth elements, and the average atomic percentage of rare earth elements in the first shell 12 is higher than the average atomic percentage of rare earth elements in the second shell 13. By satisfying that the average atomic percentage of rare earth elements in the first shell 12 is between 4.0 at% and 6.0 at%, the multilayer electronic component 100 can satisfy at least one of the following characteristics (hereinafter referred to as TCC characteristics): X5R, X6S, X7R, X7S, X7T, and X8R. This results in excellent dielectric constant and minimized dielectric loss (Dissipation Factor, DF). Furthermore, dielectric breakdown does not occur even when a high voltage of 250V or more is applied in a high-voltage environment, resulting in excellent reliability.

[0109] If the average atomic percentage of rare earth elements in the first shell 12 is less than 4.0 at%, it may be difficult to distinguish it from the second shell 13, and it may not meet the TCC characteristics. If the average atomic percentage of rare earth elements in the first shell 12 exceeds 6.0 at%, the dielectric breakdown voltage (BDV) may decrease due to reduced dispersibility of the rare earth elements.

[0110] Furthermore, by satisfying the requirement that the average atomic percentage of rare earth elements in the second shell 13 be between 2.0 at% and 4.0 at%, the TCC characteristics can be met, resulting in excellent dielectric constant and minimizing dielectric loss (DF).

[0111] If the average atomic percentage of rare earth elements in the second shell 13 is less than 2.0 at%, the TCC characteristics may not be met. If the average atomic percentage of rare earth elements in the second shell 13 is 4.0 at% or more, it may not be easy to distinguish it from the first shell 12, and the dielectric breakdown voltage (BDV) may decrease.

[0112] Furthermore, by ensuring that the average atomic percentage of rare earth elements in core 11 is between 0 at% and 2.0 at%, excellent dielectric constant can be achieved.

[0113] If the average atomic percentage of rare earth elements in core 11 is 2.0 at% or higher, the dielectric constant may decrease, potentially failing to meet the TCC (Triple Curve Compression) property requirements.

[0114] On the other hand, in the core-double-shell dielectric crystal grain 10, the average atomic percentage of titanium (Ti) in the first shell 12 may be 15 at% or more and 25 at% or less, more preferably 18 at% or more and 22 at% or less, and the average atomic percentage of titanium (Ti) in the second shell 13 may be 15 at% or more and 25 at% or less, more preferably 18 at% or more and 22 at% or less. In this case, the average atomic percentage of titanium (Ti) in the second shell 13 may be higher than the average atomic percentage of titanium (Ti) in the first shell 12.

[0115] To illustrate with more detail one embodiment of the present invention, elements were mapped to the cross-sections in the first and second directions at the center of the third direction of the main body 110 using energy-dispersive X-ray spectroscopy (EDS) mode with a transmission electron microscope (TEM) to include rare earth elements (e.g., gadolinium (Gd)) and titanium (Ti). Then, when EDS analysis was performed at five points each in the first shell 12 and the second shell 13 of the observed core-double shell structure dielectric crystal grain 10, the average atomic percentage of titanium (Ti) at the five points in the second shell 13 was 20.16 at%, and the average atomic percentage of titanium (Ti) at the five points in the first shell 12 was 19.9 at%.

[0116] Furthermore, in the core-double-shell dielectric crystal grain 10, the ratio of the average atomic percentage of titanium (Ti) to the average atomic percentage of rare earth elements in the first shell 12 can be 3 or more and 5.5 or less, and the ratio of the average atomic percentage of titanium (Ti) to the average atomic percentage of rare earth elements in the second shell 13 can be 4.5 or more and 11 or less.

[0117] The ratio of the average atomic percentage of titanium (Ti) to the average atomic percentage of rare earth elements in the first shell 12 and the second shell 13 can be calculated, for example, by the following method, but is not limited to this. First, if the average atomic percentage of rare earth elements at five locations in the first shell 12 is 5 at%, and the average atomic percentage of titanium (Ti) at five locations in the first shell 12 is 20 at%, then the ratio of the average atomic percentage of titanium (Ti) (corresponding to 20 at%) to the average atomic percentage of rare earth elements in the first shell 12 (corresponding to 5 at%) is 4. Next, if the average atomic percentage of rare earth elements at the five locations in the second shell 13 is 3 at%, and the average atomic percentage of titanium (Ti) at the five locations in the second shell 13 is 20 at%, then the ratio of the average atomic percentage of titanium (Ti) in the second shell 13 (corresponding to 20 at%) to the average atomic percentage of rare earth elements in the second shell 13 (corresponding to 3 at%) is 6.67.

[0118] On the other hand, the structure of the core-double-shell dielectric crystal grain 10 will be described more specifically with reference to Figures 6a and 6b. The dielectric crystal grain 10 of the core-double-shell structure may have a structure that includes an inner core 11 and double shells 12 and 13 surrounding at least a part of the core 11. In this case, at least a part of the core 11 may be surrounded by the first shell 12, and at least a part of the first shell 12 may be surrounded by the second shell 13, but it is not limited to this, and at least a part of the core 11 may be surrounded by the first and second shells 12 and 13 simultaneously, and at least a part of the first shell 12 may be surrounded by the second shell 13.

[0119] The first shell 12 preferably encloses 80% or more of the surface of the core 11, more preferably 90% or more of the surface of the core 11, and even more preferably encloses the entire surface of the core 11, but is not limited thereto.

[0120] Because the first shell 12 surrounds more than 80% of the surface of the core 11, the reliability of the stacked electronic component can be improved.

[0121] On the other hand, as described above, the dielectric layer 111 may contain a barium titanate (BaTiO3)-based dielectric material as the main component material and may contain the first to sixth minor component elements as minor component elements.

[0122] The first minor element may include a rare earth element comprising at least one of gadolinium (Gd), yttrium (Y), dysprosium (Dy), and terbium (Tb); the second minor element may include zirconium (Zr); the third minor element may include barium (Ba); the fourth minor element may include magnesium (Mg); the fifth minor element may include manganese (Mn); and the sixth minor element may include silicon (Si).

[0123] In this invention, the number of moles of minor components is explained based on 100 moles of titanium (Ti), but is not limited to this, and may be based on 100 moles of the main component substance (e.g., BaTiO3 system).

[0124] Furthermore, in this invention, barium (Ba), which is the third minor component element, can refer to the same element as barium (Ba) contained in the main component material (e.g., BaTiO3 system). However, in order to distinguish it from the barium (Ba) content contained in the main component material, it will be described as containing barium (Ba) as the third minor component element. Therefore, the total amount of barium (Ba) contained in the dielectric layer 111 can be said to be the sum of the barium (Ba) content from the main component material and the barium (Ba) from the third minor component element.

[0125] More specifically, the dielectric layer 111 may contain a first minor element that includes a rare earth element, and the number of moles of the first minor element per 100 moles of titanium (Ti) contained in the dielectric layer 111 may be between 4 moles and 5 moles. In other words, the number of moles of the rare earth element per 100 moles of titanium (Ti) contained in the dielectric layer 111 may be between 4 moles and 5 moles.

[0126] By satisfying the requirement that the number of moles of rare earth elements per 100 moles of titanium (Ti) contained in the dielectric layer 111 be between 4 moles and 5 moles, the TCC characteristics can be satisfied, the dielectric constant can be improved, and the decrease in dielectric loss (DF) or dielectric breakdown voltage (BDV) can be suppressed.

[0127] If the number of moles of rare earth elements per 100 moles of titanium (Ti) contained in the dielectric layer 111 is less than 4 moles, the TCC characteristics may not be met. If the number of moles of rare earth elements per 100 moles of titanium (Ti) contained in the dielectric layer 111 exceeds 5 moles, the dielectric breakdown voltage (BDV) may decrease.

[0128] On the other hand, the rare earth elements contained in the first and second shells 12 and 13 may be the same as the rare earth elements contained in the dielectric layer 111 described above. For example, the rare earth elements may include at least one of gadolinium (Gd), yttrium (Y), dysprosium (Dy), and terbium (Tb), preferably at least one of gadolinium (Gd), yttrium (Y), dysprosium (Dy), and terbium (Tb), and more preferably gadolinium (Gd), but are not particularly limited thereto.

[0129] Furthermore, in a stacked electronic component 100 according to one embodiment of the present invention, the first and second shells 12 and 13 contain zirconium (Zr), and the average atomic percentage of zirconium (Zr) in the core 11 may be 0 at% or more and less than 2.0 at%, the average atomic percentage of zirconium (Zr) in the first shell 12 may be 2.0 at% or more and less than 4.0 at%, and the average atomic percentage of zirconium (Zr) in the second shell 13 may be 4.0 at% or more and 6.0 at% or less.

[0130] If the average atomic percentage of zirconium (Zr) in the second shell 13 is between 4.0 at% and 6.0 at%, the reliability of the multilayer electronic component 100 can be improved. Furthermore, if the average atomic percentage of zirconium (Zr) in the first shell 12 is between 2.0 at% and less than 4.0 at%, the reliability of the multilayer electronic component 100 can be further improved.

[0131] In other words, the first and second shells 12 and 13 contain zirconium (Zr), and the average atomic percentage of zirconium (Zr) in the second shell 13 may be higher than the average atomic percentage of zirconium (Zr) in the first shell 12, the average atomic percentage of zirconium (Zr) in the second shell 13 may be higher than the average atomic percentage of (Zr) in the core 11, and the average atomic percentage of zirconium (Zr) in the first shell 12 may be higher than the average atomic percentage of zirconium (Zr) in the core 11.

[0132] As mentioned above, the average atomic percentage of zirconium (Zr) in the second shell 13 is higher than that of zirconium (Zr) in the first shell 12, which can further improve the reliability of the stacked electronic component 100.

[0133] Furthermore, the dielectric layer 111 may contain a second minor element, which may include zirconium (Zr), and the number of moles of the second minor element per 100 moles of titanium (Ti) contained in the dielectric layer 111 may be 6 moles or more and less than 10 moles. In other words, the number of moles of zirconium (Zr) per 100 moles of titanium (Ti) contained in the dielectric layer 111 may be 6 moles or more and less than 10 moles.

[0134] The zirconium (Zr) contained in the dielectric layer 111 can play a role in suppressing the ferroelectricity of the main component, barium titanate (BaTiO3).

[0135] The target TCC characteristics can be achieved by satisfying the requirement that the number of moles of zirconium (Zr) per 100 moles of titanium (Ti) contained in the dielectric layer 111 be between 6 moles and 10 moles.

[0136] If the number of moles of zirconium (Zr) per 100 moles of titanium (Ti) in the dielectric layer 111 is less than 6 moles, the target TCC characteristics may not be met, or the DC-bias characteristics may deteriorate. If the number of moles of zirconium (Zr) per 100 moles of titanium (Ti) in the dielectric layer 111 is 10 moles or more, the dielectric constant may deteriorate.

[0137] The dielectric layer 111 may further contain a third minor element, including barium (Ba), and the number of moles of the third minor element per 100 moles of titanium (Ti) contained in the dielectric layer 111 may be greater than or equal to the number of moles of the second minor element. For example, the number of moles of the third minor element per 100 moles of titanium (Ti) contained in the dielectric layer 111 may be between 8 moles and 11 moles. In other words, the number of moles of barium (Ba) per 100 moles of titanium (Ti) contained in the dielectric layer 111 may be between 8 moles and 11 moles.

[0138] This ensures that the number of moles of barium (Ba) per 100 moles of titanium (Ti) contained in the dielectric layer 111 is between 8 moles and 11 moles, thereby achieving the target TCC characteristics.

[0139] If the number of moles of barium (Ba) per 100 moles of titanium (Ti) in the dielectric layer 111 is less than 8 moles, the target TCC characteristics may not be met, or the DC-bias characteristics may deteriorate. If the number of moles of barium (Ba) per 100 moles of titanium (Ti) in the dielectric layer 111 exceeds 11 moles, the dielectric constant may deteriorate.

[0140] Here, the number of moles of barium (Ba) contained in the third minor component element is the value obtained by subtracting the number of moles of barium (Ba) from the main component material (e.g., BaTiO3), as mentioned above. In other words, the total number of moles of barium (Ba) contained in the dielectric layer 111 can be said to be the sum of the number of moles of barium (Ba) from the main component material (e.g., BaTiO3) and the number of moles of barium (Ba) contained in the third minor component element. As a more specific example, if the amount of barium (Ba), which is the third minor component element, is 8 moles or more and 11 moles or less per 100 moles of barium titanate (BaTiO3), then the total number of moles of barium (Ba) contained in the dielectric layer 111 may be 108 moles or more and 111 moles or less per 100 moles of titanium (Ti).

[0141] On the other hand, the average thickness of the first shell 12 may be between 20 nm and 70 nm, or the average thickness of the first shell 12 relative to the average diameter of the core 11 may be between 4% and 18%.

[0142] Here, the average diameter of the core 11 can mean the average value of the diameter passing through the center of the core 11, and the average thickness of the first shell 12 can mean the average value of the length of the first shell 12 located on the extension of the diameter passing through the center of the core 11, but is not limited to these.

[0143] By satisfying that the average thickness of the first shell 12 is 20 nm or more and 70 nm or less, or that the average thickness of the first shell 12 relative to the average diameter of the core 11 is 4% or more and 18% or less, the TCC characteristics can be satisfied, potentially improving the dielectric constant and suppressing a decrease in dielectric loss (DF) or dielectric breakdown voltage (BDV).

[0144] If the average thickness of the first shell 12 is less than 20 nm, or if the average thickness of the first shell 12 relative to the average diameter of the core 11 is less than 4%, the TCC characteristics may not be met. If the average thickness of the first shell 12 exceeds 70 nm, or if the average thickness of the first shell 12 relative to the average diameter of the core 11 exceeds 18%, the dielectric breakdown voltage (BDV) may decrease.

[0145] The present invention will be described in more detail below with reference to examples, but this is intended to aid in a concrete understanding of the invention, and the scope of the present invention is not limited by these examples.

[0146] (Examples) The dielectric layers of Samples A to F in [Table 1] contain gadolinium (Gd), the first minor component element (rare earth element), in different amounts (moles) relative to 100 moles (moles) of titanium (Ti). In other words, relative to 100 moles of Ti, Sample A contains 3.75 moles of Gd, Sample B contains 4.0 moles of Gd, Sample C contains 4.25 moles of Gd, Sample D contains 4.5 moles of Gd, Sample E contains 5.0 moles of Gd, and Sample F contains 5.5 moles of Gd.

[0147] Furthermore, the dielectric layers of Samples A to F contain the same amounts of the second minor element (Zirconium (Zr)), the third minor element (Barium (Ba)), the fourth minor element (Mg), the fifth minor element (Manganese (Mn)), and the sixth minor element (Silicon (Si)) based on 100 moles of titanium (Ti). In particular, the second minor element, Zirconium (Zr), is contained in an amount of 6 moles or more but less than 10 moles per 100 moles of Ti, and the third minor element, Barium (Ba), is contained in an amount of 8 moles or more but less than 11 moles per 100 moles of Ti.

[0148] For each raw material powder containing the types and content of titanium (Ti) and the first minor element (Gd) listed in [Table 1], and the aforementioned second to sixth minor elements, zirconia beads were used as the mixing / dispersion media. Ethanol / toluene and a dispersant were mixed and milled for 12 hours, then a binder was added and the mixture was milled for another 12 hours to produce a slurry. The produced slurry was used to produce a molded sheet with a thickness of 8 μm using a sheet manufacturing molding machine. Nickel (Ni) internal electrodes were printed on the molded sheet. The upper and lower cover sections were made by laminating 25 layers of cover molded sheets with a thickness of 10 μm to 13 μm, and a crimped bar was produced by pressing and laminating 20 layers of sheets with the nickel (Ni) internal electrodes printed on them. The crimped bar was cut into 2012 (length × width: 2.0 mm × 1.2 mm) size chips using a cutting machine. After the fabrication of the 2012-size MLCC chips was completed, they were pre-calcined, then fired in a reducing atmosphere (1.2% H2-98.8% N2) at a temperature of 1200°C to 1300°C for approximately 1 hour and 40 minutes, followed by re-oxidation in an N2 atmosphere at 1070°C for 3 hours. The fired chips were then subjected to a termination process with copper (Cu) paste and electrode firing to complete the external electrodes, and MLCC samples were prepared.

[0149] After firing, the dielectric layer thickness was approximately 7.3 μm, and 20 dielectric layers were fabricated, interposed between the internal electrodes.

[0150] [Table 1]

[0151] Table 2 below shows the characteristics of each sample from sample groups A to F, after firing raw materials containing the components of samples A to F from Table 1 at temperatures ranging from 1100°C to 1300°C. Samples with different numbers within the same sample group, such as samples A-1 to A-5, were fired at different temperatures. This is also true for sample groups B and F.

[0152] The dielectric constant and dielectric loss were determined by measuring the capacitance of prototype MLCC samples fabricated using the method described above, under conditions of 1 kHz and AC 1 V, using an LCR meter. Subsequently, the dielectric constant of the dielectric was calculated from the capacitance, dielectric layer thickness, internal electrode area, and number of layers. A dielectric constant of 900 or higher was evaluated as good, and a dielectric constant below 900 was evaluated as poor.

[0153] TCC characteristics were measured by taking the capacitance value at 25°C as the baseline and measuring the change in capacitance with temperature in the temperature range of -55°C to 125°C, and recording the result as a percentage (%). Samples that met the X7T characteristic (a characteristic where the capacitance change rate from -55°C to 125°C is between -33% and 22%, based on the capacitance at 25°C) were evaluated as good, and samples that did not meet the X7T characteristic were evaluated as poor.

[0154] Step-IR involves applying a voltage to a sample while gradually increasing it at a temperature of 150°C. Specifically, a DC voltage of 15V / μm is applied for 10 minutes, and then an additional electric field of approximately 15V / μm is applied in steps, increasing at 10-minute intervals, until the insulation resistance (IR) reaches 10. 5 The step at which the resistance dropped below Ω was measured and recorded. For example, in sample A-1, when 15V / μm was applied for 10 minutes (1-step) and the voltage was increased in two steps of 15V / μm each, the insulation resistance was 10 5 Since the voltage dropped below Ω, it was described as 3-step. At this time, samples with a voltage step of 6-step or more were evaluated as good, and samples with 5-step or less were evaluated as poor.

[0155] In the characteristic evaluation, "O" was written if the dielectric constant, X7T characteristics, and Step-IR evaluation were all evaluated as good, and "X" was written if even one of the dielectric constant, X7T characteristics, or Step-IR evaluation was evaluated as poor.

[0156] [Table 2]

[0157] In samples B-1, B-2, B-3, C-1, D-1, and E-1, the average atomic percentage of gadolinium (Gd) in the first shell was measured to be between 4.0 at% and 6.0 at%, which was higher than the average atomic percentage of gadolinium (Gd) in the second shell. This indicates that, depending on the gadolinium (Gd) content in the raw material powder, core-double-shell dielectric crystal grains may or may not be realized in which the average atomic percentage of gadolinium (Gd) in the first shell is formed to be between 4.0 at% and 6.0 at%, and higher than the average atomic percentage of gadolinium (Gd) in the second shell.

[0158] Figure 7 shows an image of the gadolinium (Gd) element mapped onto the core-double-shell dielectric crystal grains of sample D-1 via scanning transmission electron microscopy (STEM) EDS mode, and Figure 8 is a graph of the atomic percentage of gadolinium (Gd) measured by line profiling along the LP-LP' line in Figure 7.

[0159] More specifically, STEM-EDS analysis confirms that a single dielectric crystal grain contains a core region mainly composed of BaTiO3 and a shell region containing minor constituent elements. In this case, when the image is mapped using gadolinium (Gd) as a reference, the region where the average atomic percentage of gadolinium (Gd) is between 4at% and 6at% corresponds to the first shell, the region where the average atomic percentage of gadolinium (Gd) is between 2at% and 4at% corresponds to the second shell, and the region where the average atomic percentage of gadolinium (Gd) is between 0at% and 2at% corresponds to the core.

[0160] Based on the analysis of the line profiles, it was determined that the region where the average atomic percentage of gadolinium (Gd) is between 4at% and 6at% corresponds to the first shell, the region where the average atomic percentage of gadolinium (Gd) is between 2at% and 4at% corresponds to the second shell, and the region where the average atomic percentage of gadolinium (Gd) is between 0at% and 2at% corresponds to the core.

[0161] Although not attached to the diagram, in the case of sample A-4, regions with an average atomic percentage of gadolinium (Gd) between 2at% and less than 4at% were widely distributed in the shell region, making it difficult to distinguish between the first and second shells. In contrast, in the case of samples B-3 and D-1, which had similar firing temperatures to sample A-4 but contained more gadolinium (Gd), regions with an average atomic percentage of gadolinium (Gd) between 4at% and 6at% were detected at the core-shell interface of the core-shell structured BaTiO3 crystal grains, confirming the formation of the first shell.

[0162] Furthermore, in sample groups B to E, when the average atomic percentage of gadolinium (Gd) in the first shell is measured to be between 4.0 at% and 6.0 at%, and is higher than the average atomic percentage of gadolinium (Gd) in the second shell, the DF (%) value is relatively low, indicating improved dielectric loss.

[0163] As described above, embodiments of the present invention have been explained in detail, but the present invention is not limited by the embodiments described above and the accompanying drawings, but is limited by the claims provided. Therefore, within the scope of the technical idea of ​​the present invention as described in the claims, various forms of substitution, modification, and alteration are possible by persons with ordinary skill in the art, and these also fall within the scope of the present invention.

[0164] Furthermore, the expression "one embodiment" as used in this invention does not mean that each embodiment is the same as another, but is provided to emphasize and describe the unique and distinct features of each embodiment. However, the above-presented embodiments do not preclude their realization in combination with the features of other embodiments. For example, even if a matter described in a particular embodiment is not described in another embodiment, it can be understood as a description related to the other embodiment, as long as there is no description in the other embodiment that contradicts or is contrary to that matter.

[0165] The terms used in this invention are used solely to describe one embodiment and are not intended to limit the invention. In this context, singular expressions include plural expressions unless the context clearly indicates a different meaning. [Explanation of Symbols]

[0166] 10: Core-Double Shell Dielectric Crystal Grains 11: Core 12: First Shell 13: Second Shell 20: Core-shell dielectric crystal grains 21: Core 22: Shell 30: Dielectric crystal grains 100: Stacked Electronic Components 110: Main unit 111: Dielectric layer 112, 113: Cover section 114, 115: Side margin section 121, 122: Internal electrode 131, 132: External electrodes

Claims

1. A main body including a dielectric layer and internal electrodes, The body includes an external electrode disposed on the main body, The dielectric layer comprises a plurality of dielectric crystal grains, At least one of the plurality of dielectric crystal grains has a core-double shell structure including a core, a first shell surrounding at least a portion of the core, and a second shell surrounding at least a portion of the first shell. The first and second shells contain rare earth elements, and the average atomic percentage of rare earth elements in the first shell is higher than the average atomic percentage of rare earth elements in the second shell. A multilayer electronic component wherein the average atomic percentage of rare earth elements in the first shell is 4.0 at% or more and 6.0 at% or less.

2. The stacked electronic component according to claim 1, wherein the average atomic percentage of rare earth elements in the second shell is 2.0 at% or more and less than 4.0 at%.

3. The stacked electronic component according to claim 1, wherein the average atomic percentage of rare earth elements in the core is 0 at% or more and less than 2.0 at%.

4. The dielectric layer contains rare earth elements and titanium (Ti), The laminated electronic component according to claim 1, wherein the number of moles of rare earth elements per 100 moles of titanium (Ti) contained in the dielectric layer is 4 moles or more and 5 moles or less.

5. The multilayer electronic component according to claim 1, wherein the rare earth element includes at least one of gadolinium (Gd), yttrium (Y), dysprosium (Dy), and terbium (Tb).

6. The stacked electronic component according to claim 1, wherein the first and second shells contain zirconium (Zr), and the average atomic percentage of zirconium (Zr) in the second shell is higher than the average atomic percentage of zirconium (Zr) in the first shell.

7. The stacked electronic component according to claim 1, wherein the first and second shells contain zirconium (Zr), and the average atomic percentage of zirconium (Zr) in the second shell is 4.0 at% or more and 6.0 at% or less.

8. The stacked electronic component according to claim 1, wherein the first and second shells contain zirconium (Zr), and the average atomic percentage of zirconium (Zr) in the first shell is 2.0 at% or more and less than 4.0 at%.

9. The dielectric layer comprises zirconium (Zr) and titanium (Ti). The laminated electronic component according to claim 1, wherein the number of moles of zirconium (Zr) per 100 moles of titanium (Ti) contained in the dielectric layer is 6 moles or more and less than 10 moles.

10. The stacked electronic component according to claim 1, wherein the average thickness of the first shell is 20 nm or more and 70 nm or less.

11. The stacked electronic component according to claim 1, wherein the average thickness of the first shell is 4% or more and 18% or less of the average diameter of the core.

12. The stacked electronic component according to claim 1, wherein the first shell surrounds 80% or more of the surface of the core.

13. The stacked electronic component according to claim 1, wherein the main body includes a plurality of dielectric layers, and at least one of the plurality of dielectric layers has an average thickness of 10.0 μm or less.

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