Multilayer electronic component

Abstract

To provide a multilayer electronic component having improved reliability.SOLUTION: A multilayer electronic component according to one embodiment of the present invention includes: a body including a dielectric layer 111 and internal electrodes 121, 122; and external electrodes disposed on the body. When the average thickness of the dielectric layer is defined as td μm, the dielectric layer includes five or more secondary phases 141a which each include Si and have a cross-sectional area of 0.01 μm2 or more within a td μm×td μm region. In the multilayer electronic component according to one embodiment of the present invention, the dielectric layer may include five or less secondary phases which each include Si and have a cross-sectional area of less than 0.01 μm2 within a 1 μm×1 μm region. In the multilayer electronic component according to one embodiment of the present invention, the average atomic percentage of Si of the secondary phase including Si may be 5 at % or more and 20 at % or lower.SELECTED DRAWING: Figure 5

Description

Technical Field

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

Background Art

[0002] A multilayer ceramic capacitor (MLCC), which is one type of multilayer electronic component, is a chip-type capacitor that is mounted on a printed circuit board of various electronic products such as video devices like liquid crystal display (LCD) and plasma display panel (PDP), computers, smartphones, and mobile phones, and serves to charge or discharge electricity.

[0003] Such a multilayer ceramic capacitor can be used as a component of various electronic devices due to its advantages of being small in size while ensuring high capacitance and being easy to mount. As various electronic devices such as computers and mobile devices are miniaturized and have increased output, the requirements for miniaturization and high capacitance of multilayer ceramic capacitors are increasing.

[0004] As the market for MLCCs used in electronics not only for IT but also for automotive applications expands, the demand for products with higher rated voltages and excellent reliability in the same capacitance range is increasing. Generally, it is known that the smaller the grain size and the more grain boundaries there are in the dielectric, the higher the reliability of the dielectric. Among the additive elements in the MLCC dielectric composition, the effects of valence-fixed acceptors, transition metal elements which are valence-variable acceptors, and rare earth elements on reliability are known. Generally, by optimizing the composition ratios of these dielectric additive elements, conditions with good reliability are selected. Since more than 30 years have passed since the industrialization of BME (Base Metal Electrode) MLCCs, composition optimization work for improving reliability has been continuously carried out, and many such cases have already been reported as patents. Recently, it has been reported that even with the same dielectric composition, there are significant differences in reliability depending on the microstructure, the distribution and solid solution degree of additive elements, and process conditions, and research on this is actively underway.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] One of the several problems to be solved by the present invention is to provide a multilayer electronic component with improved reliability.

[0007] One of the several problems to be solved by the present invention is to provide a multilayer electronic component that satisfies X7R or X7S characteristics.

[0008] One of the several problems to be solved by the present invention is to provide a multilayer electronic component with improved accelerated life at high temperature and high pressure.

[0009] One of the problems to be solved by the present invention is to provide a multilayer electronic component with improved capacitance.

[0010] However, several problems to be solved by the present invention are not limited to the above-described content, and can be more easily understood in the process of explaining specific embodiments of the present invention.

Means for Solving the Problems

[0011] A multilayer electronic component according to an embodiment of the present invention includes a main body including a dielectric layer and an internal electrode, and an external electrode disposed on the main body. When the average thickness of the dielectric layer is td μm, the dielectric layer has a cross-sectional area of 0.01 μm 2 or more and can include five or more secondary phases containing Si in a region of td μm × td μm.

Effects of the Invention

[0012] One of the effects of the present invention is to improve the reliability of the multilayer electronic component.

[0013] One of the effects of the present invention is to satisfy the X7R or X7S characteristics of the multilayer electronic component.

[0014] One of the effects of the present invention is to improve the accelerated life of the multilayer electronic component at high temperature and high pressure.

[0015] One of the effects of the present invention is to improve the capacitance of the multilayer electronic component.

[0016] However, the various but 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 specific embodiments of the present invention.

Brief Description of the Drawings

[0017]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Mode for Carrying Out the Invention

[0018] 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. Further, 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 the elements in the drawings can be exaggerated for a clearer explanation, and the elements indicated by the same reference numerals in the drawings are the same elements.

[0019] 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 the respective configurations 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 concept 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.

[0020] 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.

[0021] Multilayer electronic component FIG. 1 schematically shows a perspective view of a multilayer electronic component according to an embodiment of the present invention. FIG. 2 schematically shows a separated perspective view showing the stacked structure of internal electrodes. FIG. 3 schematically shows a cross-sectional view taken along line I-I' of FIG. 1. FIG. 4 schematically shows a cross-sectional view taken along line II-II' of FIG. 1. FIG. 5 schematically shows an enlarged view of the P region in FIG. 3. FIG. 6 schematically shows an enlarged view of the PM region in FIG. 5. FIG. 7 schematically shows a schematic diagram of core-shell dielectric crystal grains.

[0022] Hereinafter, with reference to FIGS. 1 to 7, a multilayer electronic component according to an embodiment of the present invention will be described in detail. However, although a multilayer ceramic capacitor will be described as an example of the multilayer electronic component, the present invention can also be applied to various electronic products using a dielectric composition, such as inductors, piezoelectric elements, varistors, or thermistors.

[0023] A multilayer electronic component 100 according to an embodiment of the present invention includes a main body 110 including dielectric layers 111 and internal electrodes 121 and 122, and external electrodes 131 and 132 disposed on the main body 110. When the average thickness of the dielectric layer 111 is td μm, the dielectric layer 111 can include five or more secondary phases 141a having a cross-sectional area of 0.01 μm 2 or more and containing Si in the region of td μm × td μm.

[0024] The main body 110 may have the dielectric layers 111 and the internal electrodes 121 and 122 alternately stacked.

[0025] More specifically, the main body 110 can include a capacitance forming portion Ac that is disposed inside the main body 110 and includes a first internal electrode 121 and a second internal electrode 122 that are alternately disposed so as to face each other with the dielectric layer 111 interposed therebetween to form a capacitance.

[0026] There is no particular limitation on the specific shape of the main body 110. However, 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 particles contained in the main body 110 during the firing process, the main body 110 does not have a hexahedron shape with perfect straight lines, but can have a substantially hexahedron shape.

[0027] 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 surface 1 and the second surface 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, 4 and face each other in a third direction.

[0028] 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).

[0029] 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.

[0030] In addition, various ceramic additives, organic solvents, binders, dispersants, etc. can be added to particles such as barium titanate (BaTiO3) as the raw material for forming the dielectric layer 111 according to the object of the present invention.

[0031] Note that since the dielectric layer 111 can be formed using a dielectric material such as barium titanate (BaTiO3), it can contain a dielectric microstructure after firing. The dielectric microstructure can include a plurality of crystal grains, grain boundaries disposed between the adjacent crystal grains, and triple points disposed at points where three or more of the grain boundaries meet, and each can include a plurality of them.

[0032] In addition, at least one of the plurality of crystal grains can include a core-shell dielectric crystal grain 10 having a structure of a core 11 and a shell 12 surrounding at least a part of the core 11, and can include dielectric crystal grains that do not have a core-shell structure, but is not particularly limited thereto.

[0033] The thickness td of the dielectric layer 111 does not need to be particularly limited.

[0034] In order to ensure the reliability of the multilayer electronic component 100 under a high voltage environment, the thickness of the dielectric layer 111 may be 10.0 μm or less. Also, in order 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 in order 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.

[0035] Here, the thickness td of the dielectric layer 111 can mean the thickness td of the dielectric layer 111 disposed between the first and second internal electrodes 121 and 122.

[0036] On the one hand, the thickness td of the dielectric layer 111 can mean the size of the dielectric layer 111 in the first direction. Also, the thickness td of the dielectric layer 111 can mean the average thickness td of the dielectric layer 111 and can mean the average size of the dielectric layer 111 in the first direction.

[0037] The average size of the dielectric layer 111 in the first direction can be measured by scanning an image of the cross-sections of the main body 110 in the first and second directions with a scanning electron microscope (SEM) at a magnification of 10,000 times. More specifically, the average size of one dielectric layer 111 in the first direction can mean the average value calculated by measuring the size of one dielectric layer 111 in the first direction at 10 equally spaced points in the second direction in the scanned image. The 10 equally spaced points can be specified by the capacitance forming portion Ac. Also, when such measurement of the average value is extended to 10 dielectric layers 111 to measure the average value, the average size of the dielectric layer 111 in the first direction can be further generalized.

[0038] The internal electrodes 121 and 122 may be alternately laminated with the dielectric layer 111.

[0039] The internal electrodes 121 and 122 can include a first internal electrode 121 and a second internal electrode 122. The first and second internal electrodes 121 and 122 are alternately arranged so as to face each other with the dielectric layer 111 constituting the main body 110 interposed therebetween, and can be respectively exposed on the third and fourth surfaces 3 and 4 of the main body 110.

[0040] More specifically, the first internal electrode 121 can be separated from the fourth surface 4 and exposed through the third surface 3, and the second internal electrode 122 can be separated from the third surface 3 and exposed through the fourth surface 4. A first external electrode 131 can be arranged on the third surface 3 of the main body 110 and connected to the first internal electrode 121, and a second external electrode 132 can be arranged on the fourth surface 4 of the main body 110 and connected to the second internal electrode 122.

[0041] That is, 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. At this time, the first and second internal electrodes 121 and 122 can be electrically separated from each other by the dielectric layer 111 disposed therebetween.

[0042] On the other hand, the main body 110 can be formed by alternately laminating a ceramic green sheet printed with the first internal electrode 121 and a ceramic green sheet printed with the second internal electrode 122 and then firing them.

[0043] The materials for forming the internal electrodes 121 and 122 are not particularly limited, and materials having excellent electrical conductivity can be used. For example, the internal electrodes 121 and 122 can contain 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.

[0044] Also, the internal electrodes 121 and 122 can be formed by printing a conductive paste for internal electrodes containing 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 on a ceramic green sheet. As the printing method of the conductive paste for internal electrodes, a screen printing method, a gravure printing method, or the like can be used, but the present invention is not limited thereto.

[0045] On the other hand, the thickness te of the internal electrodes 121 and 122 does not need to be particularly limited.

[0046] In order to ensure the reliability of the multilayer electronic component 100 under high voltage environments, the thickness te of the internal electrodes 121 and 122 may be 3.0 μm or less. Also, in order 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. In order 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.

[0047] 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 can mean 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.

[0048] The average size of the internal electrodes 121 and 122 in the first direction can be measured by scanning an image of the cross-section of the main body 110 in the first and second directions 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 points that are equally spaced 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.

[0049] 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.

[0050] In other words, one average thickness td of the dielectric layer 111 may be even greater than twice one average thickness te of the internal electrodes 121 and 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.

[0051] 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.

[0052] Therefore, in order to prevent the decrease in the breakdown voltage in a high-voltage environment, by making the average thickness td of the dielectric layer 111 greater than twice the average thickness te of the internal electrodes 121 and 122, the thickness of the dielectric layer, which is the distance between the internal electrodes, can be increased, and the breakdown voltage characteristics can be improved.

[0053] When 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 thin, the breakdown voltage may decrease, and there is a possibility of a short circuit occurring between the internal electrodes.

[0054] On the other hand, the main body 110 may include cover portions 112 and 113 disposed on both end-surfaces in the first direction of the capacitance forming portion Ac.

[0055] Specifically, it may include a first cover portion 112 disposed on one surface in the first direction of the capacitance forming portion Ac and a second cover portion 113 disposed on the other surface in the first direction of the capacitance forming portion Ac. More specifically, it may include an upper cover portion 112 disposed on the upper part in the first direction of the capacitance forming portion Ac and a lower cover portion 113 disposed on the lower part in the first direction of the capacitance forming portion Ac.

[0056] The upper cover part 112 and the lower cover part 113 can be formed by laminating a single dielectric layer 111 or two or more dielectric layers 111 in the first direction on the upper and lower surfaces of the capacitance forming part Ac, and can basically play a role in preventing damage to the internal electrodes 121 and 122 due to physical or chemical stress.

[0057] The upper cover part 112 and the lower cover part 113 do not include the internal electrodes 121 and 122 and can include the same material as the dielectric layer 111. That is, the upper cover part 112 and the lower cover part 113 can include a ceramic material, for example, can include a barium titanate (BaTiO3)-based ceramic material.

[0058] On the other hand, the thickness tc of the cover parts 112 and 113 does not need to be particularly limited.

[0059] However, in order to more easily achieve miniaturization and high capacitance of the multilayer electronic component, the thickness tc of the cover parts 112 and 113 may be 100 μm or less, preferably 30 μm or less, and in the case of an ultra-small product, more preferably 20 μm or less.

[0060] Here, the thickness tc of the cover parts 112 and 113 can mean the size of the cover parts 112 and 113 in the first direction. Also, the thickness tc of the cover parts 112 and 113 can mean the average thickness tc of the cover parts 112 and 113 and can mean the average size of the cover parts 112 and 113 in the first direction.

[0061] The average size of the cover parts 112 and 113 in the first direction can be measured by scanning an image of the cross-section of the main body 110 in the first and second directions with a scanning electron microscope (SEM) at a magnification of 10,000 times. More specifically, in an image of a scanned cover part, it can mean the average value calculated by measuring the size in the first direction at 10 points equally spaced in the second direction.

[0062] In addition, the average size of the cover portion in the first direction measured by the method described above can have substantially the same size as the average size of the cover portion in the first direction in the cross-sections of the main body 110 in the first and third directions.

[0063] On the other hand, the multilayer electronic component 100 can include side margin portions 114 and 115 disposed on both end surfaces of the main body 110 in the third direction.

[0064] More specifically, the side margin portions 114 and 115 can include a first side margin portion 114 disposed on the fifth surface 5 of the main body 110 and a second side margin portion 115 disposed on the sixth surface 6 of the main body 110.

[0065] As shown in the figure, the side margin portions 114 and 115 can mean the regions between the boundary surfaces of the main body 110 and the end surfaces of the first and second internal electrodes 121 and 122 in the third direction with reference to the cross-sections of the main body 110 in the first and third directions.

[0066] The side margin portions 114 and 115 are formed by applying a conductive paste to form the internal electrodes 121 and 122 except for the locations where the side margin portions 114 and 115 are formed on the ceramic green sheet applied to the capacitance forming portion Ac. After cutting so that the internal electrodes 121 and 122 after lamination are exposed on the fifth and sixth surfaces 5 and 6 of the main body 110 to suppress the step difference caused by the internal electrodes 121 and 122, a single dielectric layer 111 or two or more dielectric layers 111 can also be laminated in the third direction on both end surfaces of the capacitance forming portion Ac in the third direction.

[0067] The side margin portions 114 and 115 can basically play a role in preventing damage to the internal electrodes 121 and 122 due to physical or chemical stress.

[0068] The first side margin portion 114 and the second side margin portion 115 do not include the internal electrodes 121 and 122 and can include the same material as the dielectric layer 111. That is, the first side margin portion 114 and the second side margin portion 115 can include a ceramic material, for example, a barium titanate (BaTiO3)-based ceramic material.

[0069] On the other hand, the widths wm of the first and second side margin portions 114 and 115 do not need to be particularly limited.

[0070] However, in order to more easily achieve miniaturization and high capacitance of the multilayer electronic component 100, the widths wm of the side margin portions 114 and 115 may be 100 μm or less, preferably 30 μm or less, and in the case of a super-small product, more preferably 20 μm or less.

[0071] Here, the width wm of the side margin portions 114 and 115 can mean the size of the side margin portions 114 and 115 in the third direction. Also, the width wm of the side margin portions 114 and 115 can mean the average width wm of the side margin portions 114 and 115 and can mean the average size of the side margin portions 114 and 115 in the third direction.

[0072] The average size of the side margin portions 114 and 115 in the third direction can be measured by scanning an image of the cross-section of the main body 110 in the first and third directions with a scanning electron microscope (SEM) at a magnification of 10,000 times. More specifically, in an image obtained by scanning one side margin portion, it can mean the average value calculated by measuring the sizes in the third direction at 10 equally spaced points in the first direction.

[0073] In one embodiment of the present invention, the structure in which the multilayer electronic component 100 has two external electrodes 131 and 132 is described, but the number, shape, etc. of the external electrodes 131 and 132 can be changed according to the form of the internal electrodes 121 and 122 and other purposes.

[0074] The external electrodes 131 and 132 are disposed on the main body 110 and can be connected to the internal electrodes 121 and 122.

[0075] More specifically, the external electrodes 131 and 132 can be disposed on the third and fourth surfaces 3 and 4 of the main body 110 respectively, and can include first and second external electrodes 131 and 132 respectively connected to the first and second internal electrodes 121 and 122. That is, the first external electrode 131 can be disposed 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 disposed on the fourth surface 4 of the main body and connected to the second internal electrode 122.

[0076] Also, the external electrodes 131 and 132 can extend and be disposed on a part of the first and second surfaces 1 and 2 of the main body 110, or can extend and be disposed on a part of the fifth and sixth surfaces 5 and 6 of the main body 110. That is, the first external electrode 131 can be disposed on a part of the first, second, fifth, and sixth surfaces 1, 2, 5, 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 disposed on a part of the first, second, fifth, and sixth surfaces 1, 2, 5, 6 of the main body 110 and on the third surface 3 of the main body 110.

[0077] On the other hand, the external electrodes 131 and 132 can be formed of any material as long as it has electrical conductivity such as metal, and a specific material can be determined in consideration of electrical characteristics, structural stability, etc., and may further have a multilayer structure.

[0078] For example, the external electrodes 131 and 132 can include an electrode layer disposed on the main body 110 and a plating layer disposed on the electrode layer.

[0079] To give a more specific example of the electrode layer, the electrode layer can include first electrode layers 131a and 132a which are fired electrodes including a first conductive metal and glass, or can include second electrode layers 131b and 132b which are resin-based electrodes including a second conductive metal and resin.

[0080] Here, the conductive metals included in the first electrode layers 131a and 132a can be referred to as the first conductive metals, and the conductive metals included in the second electrode layers 131b and 132b can be referred to as the second conductive metals. At this time, the first conductive metal and the second conductive metal may be the same as or different from each other. When including a plurality of conductive metals, only some of them may include the same conductive metal, but it is not particularly limited thereto.

[0081] Also, 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.

[0082] Also, the electrode layers 131a, 132a, 131b, and 132b may be formed by a method of transferring a sheet containing a conductive metal onto the main body, or may be formed by a method of transferring a sheet containing a conductive metal onto a fired electrode.

[0083] As the conductive metal included in the electrode layers 131a, 132a, 131b, and 132b, a material excellent in electrical conductivity can be used. For example, as the conductive metal, 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 can be included, but it is not particularly limited thereto.

[0084] In one embodiment of the present invention, the electrode layers 131a, 132a, 131b, and 132b can have a two-layer structure including the first electrode layers 131a and 132a and the second electrode layers 131b and 132b. Thereby, the external electrodes 131 and 132 can include the first electrode layers 131a and 132a including the first conductive metal and glass, and the second electrode layers 131b and 132b disposed on the first electrode layers 131a and 132a and including the second conductive metal and resin.

[0085] By including glass, the first electrode layers 131a and 132a play a role in improving the bonding property with the main body 110, and by including resin, the second electrode layers 131b and 132b can play a role in improving the bending strength.

[0086] The first conductive metal included in the first electrode layers 131a and 132a is not particularly limited as long as it can be electrically connected to the internal electrodes 121 and 122 for forming capacitance. For example, it can 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.

[0087] The first electrode layers 131a and 132a can be formed by applying a conductive paste provided by adding glass frit to the first conductive metal particles and then firing.

[0088] The second conductive metal included in the second electrode layers 131b and 132b can play a role in being electrically connected to the first electrode layers 131a and 132a.

[0089] The conductive metal included in the second electrode layers 131b and 132b is not particularly limited as long as it can be electrically connected to the electrode layers 131a and 132a, and can 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.

[0090] The second conductive metal contained in the second electrode layers 131b and 132b can include one or more of spherical particles and flaky particles. That is, the second conductive metal can consist only of flaky particles, or only of spherical particles, or can be in a form in which flaky particles and spherical particles are mixed. Here, the spherical particles can include forms that are not completely spherical, for example, forms in which the length ratio of the major axis to the minor axis (major axis / minor axis) is 1.45 or less. The flaky particles mean particles having a flat and elongated form, and are not particularly limited, but for example, the length ratio of the major axis to the minor axis (major axis / minor axis) may be 1.95 or more. The lengths of the major axis and the minor axis of the above spherical particles and flaky particles can be measured from an image obtained by scanning the cross-sections in the first and second directions cut at the central part in the third direction of the multilayer electronic component with a scanning electron microscope (SEM).

[0091] The resin contained in the second electrode layers 131b and 132b can play a role in ensuring bondability and absorbing shock. The resin contained in the second electrode layers 131b and 132b is not particularly limited as long as it has bondability and shock absorbability and can be mixed with the second conductive metal particles to form a paste. For example, it can include an epoxy resin.

[0092] Also, the second electrode layers 131b and 132b can include a plurality of second conductive metal particles, an intermetallic compound, and a resin. By including the intermetallic compound, the electrical connectivity with the first electrode layers 131a and 132a can be further improved. The above intermetallic compound can play a role in connecting a plurality of metal particles to improve electrical connectivity, and can play a role in surrounding and connecting the plurality of metal particles to each other.

[0093] At this time, the intermetallic compound can contain a metal having a melting point lower than the curing temperature of the resin. That is, since the intermetallic compound contains a metal having a melting point lower than the curing temperature of the resin, the metal having a melting point lower than the curing temperature of the resin melts during the drying and curing processes, and forms a part of the metal particles and the intermetallic compound so as to surround the metal particles. At this time, the intermetallic compound can preferably contain a low melting point metal of 300 °C or lower.

[0094] For example, Sn having a melting point of 213 to 220 °C can be included as the intermetallic compound. Sn melts during the drying and curing processes, and the melted Sn wets high melting point metal particles such as Ag, Ni, or Cu by capillary action, and reacts with a part of the Ag, Ni, or Cu metal particles to form intermetallic compounds such as Ag3Sn, Ni3Sn4, Cu6Sn5, and Cu3Sn. Ag, Ni, or Cu that did not participate in the reaction remains in the form of metal particles.

[0095] Therefore, the plurality of second conductive metal particles can contain one or more of Ag, Ni, and Cu, and the intermetallic compound can contain one or more of Ag3Sn, Ni3Sn4, Cu6Sn5, and Cu3Sn.

[0096] The plating layers 131c and 132c can play a role in improving the mounting characteristics.

[0097] The types of the 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 may be formed of a plurality of layers.

[0098] More specific examples of the plating layers 131c and 132c are as follows. The plating layers 131c and 132c may be Ni plating layers or Sn plating layers, or may be in a form in which a Ni plating layer and an Sn plating layer are sequentially formed on the electrode layer, or may be in a form in which an Sn plating layer, a Ni plating layer, and an Sn plating layer are sequentially formed. Further, the plating layers 131c and 132c may include a plurality of Ni plating layers and / or a plurality of Sn plating layers.

[0099] The size of the multilayer electronic component 100 is not particularly limited.

[0100] However, in order to simultaneously achieve miniaturization and high capacity, the thicknesses of the dielectric layer and the internal electrodes must be reduced and the number of laminations must be increased. Therefore, the effects of the present invention can be more remarkable in the multilayer electronic component 100 having a size of 3216 (length × width: 3.2 mm × 1.6 mm) or less.

[0101] Hereinafter, the multilayer electronic component 100 according to an embodiment of the present invention will be described more specifically.

[0102] On the other hand, in the present invention, the dielectric layer 111 can include a secondary phase 141 containing Si. More specifically, the secondary phase 141 containing Si can include a secondary phase 141a having a cross-sectional area of 0.01 μm 2 or more and a secondary phase 141b having a cross-sectional area of less than 0.01 μm 2 and containing Si. However, unless there are special circumstances, the description of the secondary phase 141 containing Si can apply to the description of the secondary phase 141a having a cross-sectional area of 0.01 μm 2 or more and containing Si and the secondary phase 141b having a cross-sectional area of less than 0.01 μm 2 and containing Si.

[0103] In the multilayer electronic component 100 according to an embodiment of the present invention, when the average thickness of the dielectric layer 111 is td μm, the dielectric layer 111 can include five or more secondary phases 141a having a cross-sectional area of 0.01 μm 2 or more and containing Si in a region of td μm × td μm.

[0104] The dielectric layer 111 contains 5 or more secondary phases 141a with a cross-sectional area of 0.01 μm 2 or more and containing Si within a region of td μm × td μm, thereby improving the high-temperature accelerated life reliability. More specifically, regarding the high-temperature accelerated life reliability, for example, it can satisfy the characteristic that the mean time to failure (MTTF) under the temperature condition of 150°C and the electric field condition of 10 V / μm is 100 hours or more.

[0105] In addition to improving the high-temperature accelerated life reliability, it can satisfy at least one of the following characteristics: the room-temperature dielectric constant is 2200 or more, the dielectric loss is 10% or less, the insulation resistance at 150°C is 1.0E+6 Ω or more, the capacitance change rate from -55°C to 125°C based on the capacitance at 25°C is 15% or less, the DC-bias change rate under the electric field condition of 10 V / μm is 70% or less, and the mean time to failure (MTTF) under the temperature condition of 150°C and the electric field condition of 10 V / μm is 100 hours or more.

[0106] To improve the high-temperature accelerated life reliability, the upper limit of the number of secondary phases 141a with a cross-sectional area of 0.01 μm 2 or more and containing Si within the region of td μm × td μm of the dielectric layer 111 is not particularly limited. To prevent other characteristics from degrading, the number of secondary phases 141a with a cross-sectional area of 0.01 μm 2 or more and containing Si within the region of td μm × td μm of the dielectric layer 111 can be 53 or less.

[0107] When the dielectric layer 111 contains less than 5 secondary phases 141a with a cross-sectional area of 0.01 μm 2 or more and containing Si within a region of td μm × td μm, the high-temperature accelerated life reliability may decrease.

[0108] In the present invention, as an example of a more specific method for measuring the content of elements included in each component of the multilayer 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, in the region to be measured, a thin analysis sample thinned using a Focused Ion Beam (FIB) equipment is prepared. Then, the damaged layer on the surface of the thinned sample is removed using xenon (Xe) or argon (Ar) ion milling, and then, qualitative / quantitative analysis is performed by mapping each component to be measured with the image obtained using SEM-EDS, TEM-EDS, or STEM-EDS. In this case, the qualitative / quantitative analysis graph of each component can also be expressed in terms of the mass percentage (wt%), atomic percentage (at%), or molar percentage (mol%) of each element. At this time, the molar number of one specific component relative to the molar number of another specific component can be converted and expressed.

[0109] As yet another method, the chip is pulverized to select the region to be measured, and for the portion containing the dielectric microstructure thus selected, the components of the corresponding region can be analyzed using devices such as an inductively coupled plasma optical emission spectrometer (ICP-OES) and an inductively coupled plasma mass spectrometer (ICP-MS).

[0110] Taking, for example, FIGS. 5 and 6 which schematically show a cross-section of a capacitance forming portion according to an embodiment of the present invention, and FIG. 8 which is an image obtained by mapping Si in an EDS mode after obtaining an image of a cross-section of a capacitance forming portion according to an embodiment of the present invention using TEM, a method for measuring a secondary phase 141 containing Si will be described more specifically. When mapping Si in an EDS mode of SEM, TEM, or STEM for cross-sections in the first and second directions at the center in the third direction of the main body 110, a collective region of Si observed in the dielectric layer 111 can be defined as a secondary phase 141 containing Si.

[0111] That is, when the average thickness of the dielectric layer 111 is td μm, within a region of td μm × td μm of the dielectric layer 111, the cross-sectional area is 0.01 μm 2 or more and containing five or more secondary phases 141a containing Si means that in an image obtained by photographing cross-sections in the first and second directions at the center in the third direction of the main body 110 with SEM, TEM, or STEM, the average thickness (average size in the first direction) of the dielectric layer 111 can be defined as td μm. When mapping Si in an EDS mode in an image obtained by photographing with SEM, TEM, or STEM, within a region (area) of the dielectric layer 111 having a size of td μm in the first direction and a size of td μm in the second direction, the cross-sectional area is 0.01 μm 2 or more and can mean containing five or more secondary phases 141a containing Si.

[0112] At this time, it is not necessary to satisfy the condition that within a region of td μm × td μm of the dielectric layer 111 in all regions of the dielectric layer 111, the cross-sectional area is 0.01 μm 2 or more and containing five or more secondary phases 141a containing Si. In any region of td μm × td μm of the dielectric layer 111, the cross-sectional area is 0.01 μm 2 or more and when five or more secondary phases 141a containing Si are included, the high-temperature accelerated life reliability can be improved. However, within a region of td μm × td μm of the dielectric layer 111 in all regions of the dielectric layer 111, the cross-sectional area is 0.01 μm2 It is preferable that there are five or more secondary phases 141a containing Si and having the above properties.

[0113] Here, the cross-sectional area is 0.01 μm 2 The cross-sectional area of the secondary phase 141a containing Si and having the above properties can be measured by applying the program filter function of "Image Pro Plus", which is an image analysis program, after removing the noise of Si in the periphery other than the secondary phase 141a containing Si and having the cross-sectional area of 0.01 μm or more, but it is not particularly limited thereto. 2 It can be measured after removing the noise of Si in the periphery other than the secondary phase 141a containing Si and having the cross-sectional area of 0.01 μm or more, but it is not particularly limited thereto.

[0114] Such a method for measuring the cross-sectional area of the secondary phase 141a containing Si and having the cross-sectional area of 0.01 μm or more can be similarly applied to the secondary phase 141b containing Si and having the cross-sectional area of less than 0.01 μm, which can be said to be obvious to an ordinary technician. 2 The method for measuring the cross-sectional area of the secondary phase 141a containing Si and having the cross-sectional area of 0.01 μm or more will be described later. 2 It can be said to be obvious to an ordinary technician that it can be similarly applied to the secondary phase 141b containing Si and having the cross-sectional area of less than 0.01 μm.

[0115] In the present invention, the "secondary phase" can mean particles or segregation having a composition or crystal lattice different from that of perovskite (ABO3) dielectric particles, and can mean an aggregate of components not dissolved in the dielectric crystal grains, but is not particularly limited thereto.

[0116] That is, the secondary phase can mean an aggregate of elements not dissolved or substituted in the crystal lattice structure of the crystal grains of the barium titanate (BaTiO3)-based dielectric material. The secondary phase 141 containing Si can mean an aggregate of elements containing Si not dissolved or substituted in the crystal lattice structure of the dielectric crystal grains mainly composed of barium titanate (BaTiO3).

[0117] Further, the dielectric layer 111 can contain five or less secondary phases 141b containing Si and having a cross-sectional area of less than 0.01 μm in a region of 1 μm × 1 μm. 2 It can contain five or less secondary phases 141b containing Si and having a cross-sectional area of less than 0.01 μm.

[0118] The dielectric layer 111 contains 5 or fewer secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si within a 1 μm × 1 μm region, thereby enabling further improvement in high-temperature accelerated life reliability. To give a more specific example of the further improved high-temperature accelerated life reliability, it can satisfy the characteristic that the mean time to failure (MTTF) under a temperature condition of 150°C and an electric field condition of 10 V / μm is 200 hours or more. 2 For improving the high-temperature accelerated life reliability, the lower limit of the number of secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si within a 1 μm × 1 μm region of the dielectric layer 111 is not particularly limited. However, in order to prevent other characteristics from degrading, the number of secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si within a 1 μm × 1 μm region of the dielectric layer 111 may be 1 or more.

[0119] For improving the high-temperature accelerated life reliability, within a 1 μm × 1 μm region of the dielectric layer 111, the lower limit of the number of secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si is not particularly limited. 2 For improving the high-temperature accelerated life reliability, the lower limit of the number of secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si within a 1 μm × 1 μm region of the dielectric layer 111 is not particularly limited. However, in order to prevent other characteristics from degrading, the number of secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si within a 1 μm × 1 μm region of the dielectric layer 111 may be 1 or more. 2 For improving the high-temperature accelerated life reliability, the lower limit of the number of secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si within a 1 μm × 1 μm region of the dielectric layer 111 is not particularly limited. However, in order to prevent other characteristics from degrading, the number of secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si within a 1 μm × 1 μm region of the dielectric layer 111 may be 1 or more.

[0120] When Si is mapped in EDS mode in an image obtained by photographing the cross-section in the first and second directions at the center of the main body 110 in the third direction using SEM, TEM, or STEM, it can be meant that within a region (area) of the dielectric layer 111 having a size of 1 μm in the first direction and a size of 1 μm in the second direction, there are 5 or fewer secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si. 2 When Si is mapped in EDS mode in an image obtained by photographing the cross-section in the first and second directions at the center of the main body 110 in the third direction using SEM, TEM, or STEM, it can be meant that within a region (area) of the dielectric layer 111 having a size of 1 μm in the first direction and a size of 1 μm in the second direction, there are 5 or fewer secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si.

[0121] At this time, in all regions of the dielectric layer 111, it is not necessary to satisfy the condition of containing 5 or fewer secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si within a 1 μm × 1 μm region of the dielectric layer 111. When there are 5 or fewer secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si within an arbitrary 1 μm × 1 μm region of the dielectric layer 111, the high-temperature accelerated life reliability can be further improved. However, in all regions of the dielectric layer 111, within a 1 μm × 1 μm region of the dielectric layer 111, 2 At this time, in all regions of the dielectric layer 111, it is not necessary to satisfy the condition of containing 5 or fewer secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si within a 1 μm × 1 μm region of the dielectric layer 111. When there are 5 or fewer secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si within an arbitrary 1 μm × 1 μm region of the dielectric layer 111, the high-temperature accelerated life reliability can be further improved. However, in all regions of the dielectric layer 111, within a 1 μm × 1 μm region of the dielectric layer 111, 2 At this time, in all regions of the dielectric layer 111, it is not necessary to satisfy the condition of containing 5 or fewer secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si within a 1 μm × 1 μm region of the dielectric layer 111. When there are 5 or fewer secondary phases 141b with a cross-sectional area of less than 0.01 μm and containing Si within an arbitrary 1 μm × 1 μm region of the dielectric layer 111, the high-temperature accelerated life reliability can be further improved. However, in all regions of the dielectric layer 111, within a 1 μm × 1 μm region of the dielectric layer 111, 2It is preferable that the number of secondary phases 141b containing Si is less than 5.

[0122] At this time, the dielectric layer 111 has a cross-sectional area of ​​0.01 μm within an area of ​​td μm × td μm. 2 The secondary phase 141a containing Si is five or more, and a cross-sectional area of ​​0.01 μm is within a 1 μm×1 μm region of the td μm×td μm region. 2 When the number of secondary phases 141b containing Si is less than 5, the high temperature accelerated life reliability can be further improved.

[0123] On the other hand, the secondary phase 141 containing Si may have a composition different from that of the barium titanate (BaTiO3)-based dielectric crystal grains, and may represent yet another phase or grain that is not dissolved in the crystal lattice of the barium titanate (BaTiO3)-based dielectric crystal grains.

[0124] For example, as described above, the dielectric layer 111 may include a core-shell dielectric crystal grain 10 having a core 11 and a shell 12 structure surrounding at least a part of the core 11. In this case, the core 11 or the shell 12 may include Si, and the average atomic percentage of Si in the secondary phase 141 containing Si may be higher than the average atomic percentage of Si in the core 11, or the average atomic percentage of Si in the secondary phase 141 containing Si may be higher than the average atomic percentage of Si in the shell 12. In addition, the average atomic percentages of Ba and Ti in the secondary phase 141 containing Si may be higher than the average atomic percentages of Ba and Ti in the core 11, or the average atomic percentages of Ba and Ti in the secondary phase 141 containing Si may be higher than the average atomic percentages of Ba and Ti in the shell 12. Furthermore, the core 11, the shell 12, or the Si-containing secondary phase 141 may contain Al, but the average atomic percentage of Al in the Si-containing secondary phase 141 may be higher than the average atomic percentage of Al in the core 11, or the average atomic percentage of Al in the Si-containing secondary phase 141 may be higher than the average atomic percentage of Al in the shell 12.

[0125] Also, here, the average atomic percentage of each element contained in the secondary phase 141 containing Si can mean the average value of the atomic percentages of each element measured at three or more points within one region of the secondary phase 141 containing Si, and the average atomic percentage of each element contained in the core 11 or the shell 12 can mean the average value of the atomic percentages of each element measured at five or more points of each element contained in the same core 11 or shell 12, but is not particularly limited thereto.

[0126] More specifically, the average atomic percentage of Si in the secondary phase 141 containing Si may be 5 at% or more and 20 at% or less, and preferably 8 at% or more and 16 at% or less.

[0127] By satisfying that the average atomic percentage of Si in the secondary phase 141 containing Si is 5 at% or more and 20 at% or less, the high-temperature accelerated life reliability can be improved.

[0128] When the average atomic percentage of Si in the secondary phase 141 containing Si is less than 5 at%, the high-temperature accelerated life reliability may decrease or the insulation resistance may decrease. When the average atomic percentage of Si in the secondary phase 141 containing Si exceeds 20 at%, although it is excellent in high-temperature accelerated life reliability, the room-temperature dielectric constant may decrease.

[0129] On the other hand, the average diameter of the plurality of dielectric crystallites contained in the dielectric layer 111 may be 150 nm or more and 220 nm or less.

[0130] This may correspond to the result of firing a powder having a base material size of 100 nm, but is not particularly limited thereto.

[0131] By satisfying that the average diameter of the plurality of dielectric crystallites contained in the dielectric layer 111 is 150 nm or more and 220 nm or less, the high-temperature accelerated life reliability can be further improved, and the room-temperature dielectric constant, dielectric loss (DF), insulation resistance (IR), or DC-bias characteristics can be excellent.

[0132] When the average diameter of a plurality of dielectric crystallites contained in the dielectric layer 111 is less than 150 nm, the room-temperature permittivity may decrease. When the average diameter of a plurality of dielectric crystallites contained in the dielectric layer 111 exceeds 220 nm, the high-temperature accelerated life reliability may decrease, or the dielectric loss (DF), insulation resistance (IR), or DC-bias characteristics may decrease.

[0133] The average diameter of a plurality of dielectric crystallites contained in the dielectric layer 111 can correspond to, for example, the average of the diameters of a plurality of dielectric crystallites contained in the dielectric layer 111 with reference to a 10 μm × 10 μm region of the cross-section in the first and second directions at the center in the third direction of the main body 110. Here, the diameter of the dielectric crystallite can mean the size of any straight line passing through the center of the dielectric crystallite. More specifically, it can mean the size of the straight line in the first direction passing through the center of the dielectric crystallite. The average value of these can correspond to the average diameter of a plurality of dielectric crystallites, but it is not particularly limited thereto.

[0134] Also, in the core-shell dielectric crystallite 10, the diameter of the core 11 may be 90 nm or more and 140 nm or less.

[0135] In the core-shell dielectric crystallite 10, by satisfying that the diameter of the core 11 is 90 nm or more and 140 nm or less, the high-temperature accelerated life reliability can be improved, and at least one of the target room-temperature permittivity, dielectric loss (DF), insulation resistance (IR), X7R characteristics (TCC characteristics), or DC-bias characteristics can be satisfied.

[0136] In the core-shell dielectric crystallite 10, when the diameter of the core 11 is less than 90 nm, the high-temperature accelerated life reliability may decrease or the target room-temperature permittivity may not be satisfied. In the core-shell dielectric crystallite 10, when the diameter of the core 11 exceeds 140 nm, the insulation resistance (IR) may decrease.

[0137] In the core-shell dielectric crystal grains 10, the diameter of the core 11 can, for example, be based on a 10 μm × 10 μm region of the cross-section in the first and second directions at the center in the third direction of the main body 110. When mapping a rare earth element, such as dysprosium (Dy) or terbium (Tb), through the EDS mode, it can mean the size of the diameter of the core 11 of the core-shell dielectric crystal grains 10 contained in the dielectric layer 111. Here, the diameter of the core 11 can mean the size of any straight line passing through the center of the core 11. More specifically, it can mean the size of the straight line in the first direction passing through the center of the core 11, but it is not particularly limited thereto.

[0138] On the other hand, as described above, the dielectric layer 111 can contain a perovskite (ABO3) main component, such as a barium titanate (BaTiO3)-based dielectric material, as the main component, and can further contain sub-components. More specifically, it can further contain the following first to fourth sub-components.

[0139] a) First sub-component According to an embodiment of the present invention, the dielectric layer 111 can further contain a first sub-component element, and the first sub-component element can be a variable-valence acceptor element. The variable-valence acceptor element may be one or more of Mn, V, Cr, Fe, Co, Ni, Cu, Co, and Zn. Preferably, it may be at least one of Mn and V. More preferably, it may be Mn and V.

[0140] The first sub-component may be one or more of oxides or carbonates of variable-valence acceptor elements, and may be added together to the main component raw material before firing.

[0141] The variable-valence acceptor element, which is the first sub-component element, can play a role in improving the firing temperature, dielectric properties, insulation resistance (IR), and high-temperature accelerated life characteristics.

[0142] At this time, the number of moles of the first sub-component element with respect to 100 moles of Ti contained in the dielectric layer 111 can be 0.4 moles or more and 0.8 moles or less. When a plurality of first sub-component elements are added, the total content of these can be defined as the number of moles of the first sub-component element.

[0143] When the content of the first sub-component element with respect to 100 moles of Ti contained in the dielectric layer 111 is less than 0.4 moles, the insulation resistance (IR) may decrease. When the content of the first sub-component element with respect to 100 moles of Ti contained in the dielectric layer 111 exceeds 0.8 moles, the DC-bias change rate may decrease.

[0144] b) Second sub-component According to an embodiment of the present invention, the dielectric layer 111 can further contain a second sub-component element, and the second sub-component element can be Mg.

[0145] The second sub-component may be one or more of Mg oxide and carbonate, and may be added together to the main component raw material before firing.

[0146] Mg, which is the second sub-component element, can play a role in imparting reduction resistance and increasing the RC (Reliability Class) value. Here, the RC value can mean reliability depending on temperature, reliability at high temperature, reliability at high voltage, life evaluation, etc.

[0147] At this time, the number of moles of the second sub-component element with respect to 100 moles of Ti contained in the dielectric layer 111 may be more than 0 moles and 1 mole or less.

[0148] When no second sub-component element is added to the dielectric layer 111, for example, when the content of the second sub-component element with respect to 100 moles of Ti contained in the dielectric layer 111 is 0 moles, there is a risk of reduced reliability. When the content of the second sub-component element with respect to 100 moles of Ti contained in the dielectric layer 111 exceeds 1 mole, there is a risk of not satisfying the X7R temperature characteristics (the capacitance change rate at -55°C to 125°C is -15% or more and 15% or less based on the capacitance value at 25°C).

[0149] c) Third sub-component According to an embodiment of the present invention, the dielectric layer 111 can further contain a third sub-component element, and the third sub-component element can be a rare earth element. The rare earth element may include at least one of Y, Dy, Tb, Gd, Ce, Nd, La, and Yb, preferably at least one of Dy and Tb, and more preferably Dy and Tb.

[0150] The rare earth element, which is the third sub-component element, can play a role in improving the high-temperature accelerated life and can play a role in improving the reliability.

[0151] The third sub-component may be one or more of oxides and carbonates of rare earth elements, and may be added together to the main component raw material before firing.

[0152] At this time, the number of moles of the third sub-component element with respect to 100 moles of Ti contained in the dielectric layer 111 may be 2.5 moles or more and 3.5 moles or less.

[0153] When the number of moles of the third sub-component element with respect to 100 moles of Ti contained in the dielectric layer 111 is less than 2.5 moles, there is a risk of reduced high-temperature accelerated life. When the number of moles of the third sub-component element with respect to 100 moles of Ti contained in the dielectric layer 111 exceeds 3.5 moles, there is a risk of a decrease in insulation resistance (IR) due to n-type semiconductor conversion of the dielectric or a decrease in high-temperature accelerated life.

[0154] d) Fourth sub-component According to an embodiment of the present invention, the dielectric layer 111 can further contain a fourth sub-component element, and the fourth sub-component element can be Si.

[0155] The fourth sub-component may be at least one of an oxide of Si, a carbonate of Si, and a glass containing Si, and may be added together to the main component raw material before firing.

[0156] Si, which is the fourth sub-component element, can play a role as a sintering aid, can play a role in inducing grain growth of dielectric crystal grains, and can play a role in improving insulation resistance (IR) or high-temperature accelerated life.

[0157] At this time, the number of moles of the fourth sub-component element with respect to 100 moles of Ti contained in the dielectric layer 111 may be 0.8 mole or more and 2.0 moles or less.

[0158] When the number of moles of the fourth sub-component element with respect to 100 moles of Ti contained in the dielectric layer 111 is less than 0.8 mole, the insulation resistance (IR) may decrease or the high-temperature accelerated life may decrease. When the number of moles of the fourth sub-component element with respect to 100 moles of Ti contained in the dielectric layer 111 exceeds 2.0 moles, the room-temperature dielectric constant may decrease.

[0159] The multilayer electronic component 100 according to an embodiment of the present invention can satisfy the characteristic that the mean time to failure (MTTF) is 100 hours or more under the temperature condition of 150 °C and the electric field condition of 10 V / μm.

[0160] Further, the multilayer electronic component 100 according to an embodiment of the present invention has a characteristic that the room-temperature dielectric constant is 2200 or more, a characteristic that the dielectric loss is 10% or less, a characteristic that the insulation resistance at 150 °C is 1.0E+6 Ω or more, a characteristic that the capacitance change rate from -55 °C to 125 °C is 15% or less based on the capacitance at 25 °C, a characteristic that the DC-bias change rate under the electric field condition of 10 V / μm is 70% or less, and a characteristic that the mean time to failure (MTTF) under the temperature condition of 150 °C and the electric field condition of 10 V / μm is 100 hours or more. It can satisfy at least one of the characteristics.

[0161] The presence or absence of satisfaction of the characteristics will be described in more detail with reference to the following examples, which are for helping the specific understanding of the present invention and the scope of the present invention is not limited by the examples.

[0162] (Example) Tables 1, 3, and 5 list the base material size of the main component, the firing temperature, and the contents of the first to fourth sub-component elements. The unit of the base material size is nm, the firing temperature is °C, and the first to fourth sub-component elements indicate the types of additives and the number of moles of the first to fourth sub-component elements. For example, in Test Example 1-1, 0.2 mol of the first sub-component element MnO2 corresponds to 0.2 mol of Mn, 0.2 mol of the first sub-component element V2O5 corresponds to 0.2 mol of V, 0.6 mol of the second sub-component element MgCO3 corresponds to 0.6 mol of Mg, 3.0 mol of the third sub-component element Dy2O3 corresponds to 3.0 mol of Dy, 0.2 mol of the third sub-component element Tb4O7 corresponds to 0.2 mol of Tb, and 1.2 mol of the fourth sub-component element SiO2 corresponds to 1.2 mol of Si.

[0163] As the base material of the main component, BaTiO3 powders with average particle sizes of 100, 150, and 200 nm were used. Using zirconia beads as the mixing / dispersing media, the raw material powder containing sub-component elements corresponding to the compositions specified in Tables 1, 3, and 5 and the main component BaTiO3 powder were mixed with an ethanol / toluene solvent and a dispersant and milled for 10 hours. After mixing the binder, it was further milled for 5 hours to prepare a slurry. The slurry thus produced was used to produce a formed sheet with thicknesses of 3.0 μm and 10 μm using a sheet manufacturing molding machine. Thereafter, nickel (Ni) internal electrode printing was performed on the formed sheet. The upper and lower covers were produced by laminating 25 layers of cover sheets (with a thickness of 10 μm or more and 13 μm or less), and 21 printed sheets were laminated under pressure to produce a bar. The crimped bar was cut into chips with a size of 3216 (length × width: 3.2 mm × 1.6 mm) using a cutting machine. After firing the completed 3216-size MLCC chips, they were fired under the conditions of maintaining the temperature at 1150 °C to 1200 °C for 2 hours in a reducing atmosphere of 0.1% H2 / 99.9% N2 to 0.5% H2 / 99.5% N2 (H2O / H2 / N2 atmosphere), and then re-oxidized for 3 hours in an N2 atmosphere at 1000 °C. Here, a H2 concentration of 0.1% corresponds to the condition of an electromotive force of 670 mV in a measurement environment at 850 °C in an oxygen partial pressure measuring instrument, and a H2 concentration of 0.5% corresponds to the condition of an electromotive force of 760 mV. After the termination process and electrode firing with a copper (Cu) paste on the fired chips, the external electrodes were completed. As a result, an MLCC chip with a size of 3216 was produced in which the thickness of the dielectric layer after firing was approximately 2.0 μm and the number of dielectric layers between the internal electrodes was 20 layers.

[0164] In Table 2, 4, 6, A is based on the cross-sections in the first and second directions at the center of the main body in the third direction. When the average thickness of the dielectric layer in the capacitance forming portion is td, among the regions of td μm × td μm of the dielectric layer, the cross-sectional area is 0.01 μm 2This corresponds to the number of secondary phases 141a containing Si, and B is based on the cross-section in the first and second directions at the center of the main body in the third direction. Among the 1μm×1μm regions of the dielectric layer in the capacitance forming portion, the cross-sectional area is 0.01μm 2 This corresponds to the number of secondary phases 141b containing Si and having a cross-sectional area of less than 0.01μm

[0165] The dielectric constant and dielectric loss (DF) are described as follows: The capacitance or capacitance change rate of the MLCC chip at room temperature was measured using an LCR meter under the conditions of 1kHz and AC 0.5V / μm, and the dielectric constant of the MLCC chip was calculated from the capacitance, the thickness of the dielectric layer of the MLCC chip, the area of the internal electrode, and the number of stacked dielectric layers. When the dielectric constant is 2200 or more, it is evaluated as excellent, and when it is less than 2200, it is evaluated as defective. When the dielectric loss (DF) is 10% or less, it is evaluated as excellent, and when it exceeds 10%, it is evaluated as defective.

[0166] IR (room temperature insulation resistance) is described as follows: Ten samples were taken, and the insulation resistance value at a temperature of 150°C was measured. When IR is 1.0E+6Ω or more, it is evaluated as excellent, and when it is less than 1.0E+6Ω, it is evaluated as defective.

[0167] The TCC characteristic (change in capacitance with temperature) is described as follows: Based on the capacitance at 25°C, the capacitance change rate was measured in the temperature range of -55°C to 125°C. When the capacitance change rate is -15% or more and +15% or less in the temperature range of -55°C to 125°C, it is evaluated as excellent, and when it is outside this range, it is evaluated as defective.

[0168] The DC-bias change rate is described as follows: Ten samples were taken, and the capacitance change rate was described by measuring the capacitance after 60 seconds with a DC of 10V / μm applied. When the DC-bias change rate is -70% or more (that is, it means that the capacitance change reduction rate relative to the reference capacitance is -70% to 0%), it is evaluated as excellent, and when it is less than -70%, it is evaluated as defective.

[0169] The MTTF was obtained through Highly Accelerated Life Time Test (HALT). For each test case, a voltage equivalent to 40 V / μm of electric field was applied to 40 test pieces at 150°C, and the time to failure was measured to calculate the Mean Time to Failure (MTTF). If the MTTF was 100 hours or more, it was evaluated as excellent; if it was 200 hours or more, it was evaluated as very excellent; if it was less than 100 hours, it was evaluated as defective.

[0170]

Table 1

[0171]

Table 2

[0172] For Test Examples 1-1 to 3-4 in Table 1, when the total of the first sub-component elements Mn and V is 0.4 mol, the content of the second sub-component element Mg is 0.6 mol, the total of the third sub-component rare earth elements Dy and Tb is 3.2 mol, and the content of the fifth sub-component Si is 1.2 mol with respect to 100 mol of the main component BaTiO3, test examples according to the average size and firing temperature of BaTiO3 are shown. Test Examples 1-1 to 3-4 in Table 2 show the characteristics of the samples corresponding to these test examples. At a firing temperature of 1160°C for base material sizes of 100 nm, 150 nm, and 200 nm, and at a firing temperature of 1170°C for a base material size of 200 nm (Test Examples 1-1, 2-1, 3-1, 3-2), grain growth and densification did not occur sufficiently, and it was not possible to meet the target characteristics of the present invention: dielectric constant ≧ 2200, IR ≧ 1.0E+6 Ω, MTTF ≧ 100 hrs.

[0173] The microstructure, dielectric properties, and reliability characteristics change significantly depending on the firing conditions. Different from the samples at 1160 °C, when the firing temperatures are 1170 °C and 1180 °C (Test Examples 1-2, 1-3, 2-2, 2-3, 3-3), grain growth and densification occur within the normal range, and it can be seen that the dielectric constant, room-temperature IR, DC-bias change rate, MTTF, etc. are satisfied. However, a significant difference in the MTTF value appears depending on the base material size. Even at the same firing temperature, it was confirmed that the MTTF of the MLCC applying BaTiO3 with a base material size of 100 nm is twice as high as that of the MLCC applying BaTiO3 with 150 nm and 200 nm. The test examples with 10 or more A are MLCCs applying BaTiO3 with 100 nm, while the MLCCs applying BaTiO3 with 150 nm and 200 nm show a clear difference with 0 to 4 A. Also, regarding the number of B, the MLCC applying BaTiO3 with 100 nm has 2 to 3, and the MLCC applying BaTiO3 with 150 nm has 6 to 15, which also shows a large difference. It can be confirmed that the MTTF is significantly improved due to such differences in the numbers of A and B.

[0174] The MLCCs fabricated with base material sizes of 100 nm and 150 nm show that at a firing temperature of 1190 °C, due to excessive grain growth in both cases, DF > 10% and MTTF < 100 hrs, indicating that they do not meet the objectives of the present invention. In the case of the 200-nm base material MLCC, since 1190 °C is still an appropriate firing temperature, the target values of the present invention such as the dielectric constant, IR, and MTTF are reached. However, it can be confirmed that due to the use of a BaTiO3 base material with a large size, the DC-bias change rate tends to deviate from the target.

[0175]

Table 3

[0176]

Table 4

[0177] Test Examples 4-1 to 5-5 in Table 3 show test examples based on the change in the content of the fourth sub-component element with respect to 100 mol of the BaTiO3 base material as the main component and the base material size. Table 4 shows the characteristics of the samples corresponding to these Test Examples 4-1 to 5-5. When the content of Si, which is the fourth sub-component element, is 1 mol or less (Test Examples 4-1, 5-1), since the A value is low or does not exist, it was confirmed that it does not exceed 100 hours, which is the target value of the MTTF of the present invention. As the amount of Si, which is the fourth sub-component element, is increased from 1.2 mol to 2 mol (Test Examples 4-2, 4-3, 4-4, 5-2, 5-3, 5-4), the dielectric constant decreases, but it can be confirmed that it maintains 2200 or more, which is the target characteristic, and also satisfies the MTTF characteristic. Further, as a result of confirming the characteristics of the samples where the A value is 10 or more and the B value is 5 or less (Test Examples 4-2, 4-3, 4-4), it was confirmed that the MTTF characteristic increased by about 100 to 200% compared to the samples that do not satisfy the target conditions (Test Examples 5-2, 5-3, 5-4). In the case of the composition samples with an excessive addition where the content of Si, which is the fourth sub-component element, is 3 mol (Test Examples 4-5, 5-5), it can be seen that due to the influence of the fourth sub-component element Si with a high insulation resistance, the acceleration life is very high, while the dielectric constant does not reach the target characteristic.

[0178]

Table 5

[0179]

Table 6

[0180] Test Examples 6-1 to 7-4 in Table 5 show test examples based on changes in the base material size and the contents of the first sub-component element and the third sub-component element with respect to 100 mol of the BaTiO3 base material as the main component. Table 6 shows the characteristics of the samples corresponding to these Test Examples 6-1 to 7-4. Samples without the valence-variable elements Mn and V, which are the first sub-component elements, have significantly fewer trap sites inside the material, so the IR is lower than the target value of the present invention (Test Examples 6-1, 7-1). However, in Test Example 6-1, since the A value is higher and the B value is lower compared to 7-1, the MTTF was evaluated to be higher. In the case of Test Examples 6-2 to 6-4, the A value is 10 or more and the B value is 5 or less, and it was confirmed that the MTTF≧100 hrs, which is the target characteristic of the high-temperature reliability of the present invention, is satisfied. However, it was confirmed that Test Example 6-4 has a composition with an excessive input of the total sum of the first sub-component elements, and the DC-bias change rate becomes -70% or more, and the target of the present invention cannot be achieved. Test Examples 7-2 to 7-4 have the same composition as Test Examples 6-2 to 6-4, but it was confirmed that there are clear differences in the A value and the B value. That is, the conditions where the A value is 10 or more and the B value is 5 or less cannot be satisfied, and it can be seen that there is also a large difference in the high-temperature accelerated life.

[0181] Test Examples 8-1 to 9-4 show test examples based on changes in the base material size and the content of the third sub-component element. It can be seen that as the amount of the rare earth element, which is the third sub-component element, increases, the dielectric constant decreases and n-type formation occurs inside the material, resulting in a decrease in IR. However, in the evaluation of high-temperature accelerated life, it is possible to confirm the phenomenon that the mobility of oxygen vacancies is weakened and the MTTF is improved. Test Examples 8-1, 8-2, 9-1, and 9-2 are MLCC samples with a small amount of the third sub-component element added, and their high-temperature accelerated life is reduced compared to Test Examples 8-3 and 9-3 with 3 moles of the third sub-component element added. In fact, it can be confirmed that the addition of the rare earth element, which is the third sub-component element, improves the reliability. This is presumably due not only to the suppressing effect of the rare earth element on the mobility of oxygen vacancies but also to the effect of enhancing the reliability by forming a secondary phase (pyrochlore) containing the rare earth element and Si. Also, in the case of Test Example 8-3, it can be confirmed that the A value is higher than that of 9-3, and even with the same composition, the MTTF shows a difference of about 2.4 times. Samples (Test Examples 8-4 and 9-4) with 4 moles of the rare earth element, which is the third sub-component element, added show the result that the dielectric is excessively n-type and the IR deteriorates significantly, confirming that they do not meet the characteristic conditions of the present invention.

[0182] As described above, the embodiments of the present invention have been described in detail. However, the present invention is not limited by the above-described embodiments and the accompanying drawings, but is limited by the appended claims. Therefore, various forms of substitution, modification, and change are possible by those with ordinary knowledge in the technical field without departing from the technical idea of the present invention described in the claims, and this can also be said to belong to the scope of the present invention.

[0183] In addition, the expression "one embodiment" used in the present invention does not mean the same embodiment, but is provided to emphasize and explain each different unique feature. However, the above-presented one embodiment does not exclude being implemented in combination with the features of other embodiments. For example, even if a matter described in a specific one embodiment is not described in another one embodiment, it can be understood as an explanation related to the other one embodiment as long as there is no explanation contrary to or conflicting with that matter in the other one embodiment.

[0184] The terms used in the present invention are merely used to explain one embodiment and are not intended to limit the present invention. At this time, the singular expression includes the plural expression unless the context clearly indicates a different meaning.

Explanation of Reference Numerals

[0185] 10: Core-shell dielectric crystal grains 11: Core 12: Shell 100: Multilayer electronic component 110: Body 111: Dielectric layer 112, 113: Cover part 114, 115: Side margin part 121, 122: Internal electrode 131, 132: External electrode 141a, 141b: Secondary phase containing Si

Claims

1. a body including a dielectric layer and an internal electrode; an external electrode disposed on the body; When the average thickness of the dielectric layer is td μm, The dielectric layer has a cross-sectional area of ​​0.01 μm within an area of ​​td μm × td μm. ２ The laminated electronic component has five or more secondary phases containing Si.

2. The dielectric layer has a cross-sectional area of ​​0.01 μm within a region of 1 μm×1 μm. ２ The laminated electronic component according to claim 1 , wherein the number of secondary phases containing Si is less than 5.

3. 2. The multilayer electronic component according to claim 1, wherein an average atomic percentage of Si in the secondary phase containing Si is 5 at % or more and 20 at % or less.

4. the dielectric layer includes a core and a core-shell dielectric crystal grain having a shell structure surrounding at least a portion of the core; The laminated electronic component according to claim 1 , wherein an average atomic percentage of Si in the secondary phase containing Si is higher than an average atomic percentage of Si in the shell.

5. 2. The multilayer electronic component according to claim 1, wherein an average diameter of the plurality of dielectric crystal grains contained in the dielectric layer is 150 nm or more and 220 nm or less.

6. the dielectric layer includes a core and a core-shell dielectric crystal grain having a shell structure surrounding at least a portion of the core; 2. The multilayer electronic component according to claim 1, wherein the diameter of the core is not less than 90 nm and not more than 140 nm.

7. The dielectric layer is made of barium titanate (BaTiO ３ 2. The multilayer electronic component according to claim 1, comprising a polyimide-based main component.

8. The dielectric layer further includes a first minor component element, The first minor component element is one or more of Mn, V, Cr, Fe, Co, Ni, Cu, Co, and Zn; 8. The multilayer electronic component according to claim 7, wherein the number of moles of the first minor component element per 100 moles of Ti contained in the dielectric layer is 0.4 moles or more and 0.8 moles or less.

9. The dielectric layer further includes a second minor component element, The second minor component element is Mg, 8. The multilayer electronic component according to claim 7, wherein the number of moles of the second minor component element per 100 moles of Ti contained in the dielectric layer is more than 0 mole and 1 mole or less.

10. The dielectric layer further includes a third minor component element, the third minor component element is a rare earth element, 8. The multilayer electronic component according to claim 7, wherein the number of moles of said third minor component element per 100 moles of Ti contained in said dielectric layer is 2.5 moles or more and 3.5 moles or less.

11. The dielectric layer further includes a fourth minor component element, The fourth minor component element is Si, 8. The multilayer electronic component according to claim 7, wherein the number of moles of said fourth minor component element per 100 moles of Ti contained in said dielectric layer is 0.8 moles or more and 2.0 moles or less.

12. 2. The multilayer electronic component according to claim 1, wherein the td μm is 10.0 μm or less.

13. 2. The multilayer electronic component according to claim 1, wherein the multilayer electronic component satisfies the characteristic that the mean time to failure (MTTF) is 100 hours or more under a temperature condition of 150° C. and an electric field condition of 10 V / μm.

14. 2. The multilayer electronic component according to claim 1, which satisfies at least one of the following characteristics: a room temperature dielectric constant of 2200 or more; a dielectric loss of 10% or less; an insulation resistance at 150° C. of 1.0E+6Ω or more; a capacitance change rate of 15% or less at −55° C. to 125° C. based on the capacitance at 25° C.; a DC-bias change rate of 70% or less under an electric field condition of 10 V / μm; and a mean time to failure (MTTF) of 100 hours or more under a temperature condition of 150° C. and an electric field condition of 10 V / μm.

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