Laminated type electronic component

Abstract

To provide a laminated type electronic component which is excellent in high temperature reliability, moisture resistance reliability, and insulation resistance.SOLUTION: A laminated type electronic component includes a body including a dielectric layer, and an internal electrode alternately arranged with the dielectric layer, and an external electrode arranged on the body, wherein the dielectric layer includes secondary phases containing Zr and Y, in the secondary phase included in the dielectric layer, a number ratio of the secondary phases contacting the internal electrode is 70% or more. A laminated type electronic component of the invention is excellent in high temperature reliability, and moisture resistance reliability.SELECTED DRAWING: Figure 4

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-shaped capacitor 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. Such an MLCC 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.

[0003] In recent years, as the markets for IT-use and automotive-use MLCCs have expanded, the demand for products with high rated voltage and excellent reliability in the same capacitance range has been increasing. Among the elements of the MLCC dielectric composition additives, the effects of valence-fixed acceptors, transition metal elements which are valence-variable acceptors, and rare earth elements on reliability are already known, and generally, conditions with good reliability are selected through optimization of the composition ratios of these dielectric additive elements. Recently, it has been reported that even with the same dielectric composition, there are significant differences in reliability depending on the microstructure, distribution and solid solution degree of additive elements, and process conditions, and research on this is being actively carried out.

Summary of the Invention

Problems to be Solved by the Invention

[0004] One of the various objects of the present invention is to provide a multilayer electronic component excellent in high-temperature reliability and moisture resistance reliability.

[0005] One of the various objects of the present invention is to provide a multilayer electronic component having excellent insulation resistance.

[0006] However, the object of the present invention is 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.

Means for Solving the Problems

[0007] One embodiment of the present invention includes a dielectric layer, a main body including internal electrodes alternately arranged with the dielectric layer, and external electrodes arranged on the main body. The dielectric layer includes a secondary phase containing Zr and Y. Among the secondary phases contained in the dielectric layer, the proportion of the number of secondary phases in contact with the internal electrodes provides a multilayer electronic component of 70% or more.

Effects of the Invention

[0008] One of the various effects of the present invention is to provide a multilayer electronic component having excellent high-temperature reliability and moisture resistance reliability.

[0009] One of the various effects of the present invention is to provide a multilayer electronic component having excellent insulation resistance.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Best Mode for Carrying Out the Invention

[0011] 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. In addition, 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 may be enlarged or reduced (or emphasized or simplified) for clearer explanation, and elements denoted by the same reference numerals in the drawings are the same elements.

[0012] In addition, parts not related to the explanation are omitted in the drawings for clearly explaining the present invention, and the sizes and thicknesses of the illustrated components are arbitrarily shown for convenience of explanation. Therefore, the present invention is not necessarily limited by the illustration. In addition, 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 "includes" a certain component, it means that other components can be further included, rather than excluding other components, unless otherwise specifically stated to the contrary.

[0013] In the drawings, the first direction can be defined as the thickness (T) direction, the second direction as the length (L) direction, and the third direction as the width (W) direction.

[0014] Stacked electronic component FIG. 1 is a perspective view schematically showing a stacked electronic component according to an embodiment of the present invention, FIG. 2 is a cross-sectional view schematically showing a cut cross-section along the line I-I' of FIG. 1, FIG. 3 is a cross-sectional view schematically showing a cut cross-section along the line II-II' of FIG. 1, FIG. 4 is an enlarged view schematically showing the P region of FIG. 2, and FIG. 5 is an exploded perspective view schematically showing the main body of FIG. 1.

[0015] Hereinafter, with reference to FIGS. 1 to 5, a multilayer electronic component 100 according to an embodiment of the present invention will be described in detail. Further, as an example of the multilayer electronic component, a multilayer ceramic capacitor will be described, but the present invention is not limited thereto, and can also be applied to various multilayer electronic components, such as inductors, piezoelectric elements, varistors, or thermistors.

[0016] The 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 alternately arranged with the dielectric layers 111, and external electrodes 130 and 140 arranged on the main body 110. The dielectric layer 111 includes a secondary phase 11 containing Zr and Y, and the percentage ratio of the number of the secondary phase 11a in the secondary phase 11 contained in the dielectric layer 111 that contacts the internal electrodes 121 and 122 can be 70% or more.

[0017] There is no particular limitation on the specific shape of the main body 110, but as shown in the figure, the main body 110 can be formed in a hexahedron shape or a shape similar thereto. Due to the shrinkage of the ceramic powder contained in the main body 110 during the firing process and the polishing of the edge portions, the main body 110 does not have a perfect hexahedron shape with straight lines, but can have a substantially hexahedron shape.

[0018] The main body 110 can have a first surface and a second surface 1 and 2 facing each other in a first direction, a third surface and a fourth surface 3 and 4 facing each other in a second direction and connected to the first surface and the second surface 1 and 2, and a fifth surface and a sixth surface 5 and 6 facing each other in a third direction and connected to the first surface to the fourth surface 1, 2, 3, and 4. The surface roughness of at least one of the first surface to the sixth surface 1, 2, 3, 4, 5, and 6 of the main body 110 can be such that the arithmetic mean surface roughness (Ra) is 0.2 μm to 1 μm.

[0019] The main body 110 can include dielectric layers 111 and internal electrodes 121 and 122 alternately arranged with the dielectric layers 111. The plurality of dielectric layers 111 forming the main body 110 are in a fired state, and the boundary between adjacent dielectric layers 111 can be integrated so that it is difficult to confirm without using a scanning electron microscope (SEM).

[0020] The dielectric layer 111 can contain a main component having a perovskite structure represented by the general formula ABO3. The A-site element can contain, for example, one or more of Ca and Sr. The B-site element can contain Zr. Further, the B-site element can further contain Ti. The dielectric layer 111 can contain, for example, a main component represented by (Ca 1-x Sr x )(Zr 1-y Ti y )O3 (0 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.5) (hereinafter referred to as the CSZT system).

[0021] The average thickness td of the dielectric layer 111 is not particularly limited. The average thickness td of the dielectric layer 111 can be, for example, 0.1 μm to 10 μm, 0.1 μm to 5 μm, 0.1 μm to 2 μm, or 0.1 μm to 0.4 μm.

[0022] Since the dielectric layer 111 can be formed using a dielectric material represented by ABO3, it can contain a dielectric microstructure after firing. The dielectric microstructure can include a plurality of dielectric crystal grains, a crystal grain system disposed between the adjacent dielectric crystal grains, and a triple point disposed at a point where three or more of the dielectric crystal boundaries are in contact, and each can include a plurality of them.

[0023] Also, although not shown, at least one of the plurality of dielectric crystal grains can have a core-shell structure having a core and a shell surrounding at least a part of the core, but the present invention is not limited thereto.

[0024] The dielectric layer 111 can be formed by manufacturing a ceramic slurry containing a main component powder, an organic solvent, and a binder, applying and drying the slurry on a carrier film to provide a ceramic green sheet, and then firing the ceramic green sheet. As the organic solvent, ethanol / toluene or the like can be used, and as the binder, polyvinyl butyral or the like can be used, but the present invention is not limited thereto.

[0025] The internal electrodes 121 and 122 can include, for example, a first internal electrode 121 and a second internal electrode 122 that are alternately arranged in a first direction with the dielectric layer 111 interposed therebetween. That is, the first internal electrode 121 and the second internal electrode 122, which are a pair of electrodes having different polarities, can be arranged so as to face each other with the dielectric layer 111 interposed therebetween. The first internal electrode 121 and the second internal electrode 122 can be electrically separated from each other by the dielectric layer 111 disposed therebetween.

[0026] The first internal electrode 121 is spaced apart from the fourth surface 4 and can be connected to the first external electrode 130 on the third surface 3 side. The second internal electrode 122 is spaced apart from the third surface 3 and can be connected to the second external electrode 140 on the fourth surface 4 side.

[0027] The conductive metal contained in the internal electrodes 121 and 122 can be one or more of Ni, Cu, Pd, Ag, Au, Pt, Sn, W, Ti, and alloys thereof, and more preferably can contain Ni, but the present invention is not limited thereto.

[0028] The average thickness te of the internal electrodes 121 and 122 is not particularly limited. The average thickness te of the internal electrodes 121 and 122 can be, for example, 0.1 μm to 3.0 μm, 0.1 μm to 1.0 μm, or 0.1 μm to 0.4 μm.

[0029] The internal electrodes 121 and 122 can be formed by printing a conductive paste for internal electrodes containing metal powder, an organic solvent, a binder, etc. with a predetermined thickness on the ceramic green sheet to form an internal electrode pattern, and firing the internal electrode pattern. 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.

[0030] The average thickness td of the dielectric layer 111 and the average thickness te of the internal electrodes 121 and 122 respectively mean the average thicknesses of the dielectric layer 111 and the internal electrodes 121 and 122 in the first direction. The average thickness td of the dielectric layer 111 and the average thickness te of the internal electrodes 121 and 122 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 a magnification of 10,000 times. More specifically, after measuring the thicknesses at a number of points of one dielectric layer 111, for example, 30 points at equal intervals in the second direction, the average thickness td of the dielectric layer 111 can be measured by taking the average value. Also, after measuring the thicknesses at a number of points of one internal electrode 121 or 122, for example, 30 points at equal intervals in the second direction, the average thickness te of the internal electrodes 121 and 122 can be measured by taking the average value. The 30 points at equal intervals can be specified in the capacitance forming portion Ac. On the other hand, after performing such average value measurements for 10 dielectric layers 111 and 10 internal electrodes 121 and 122 respectively, and then measuring the average value, the average thickness td of the dielectric layer 111 and the average thickness te of the internal electrodes 121 and 122 can be further generalized.

[0031] The main body 110 can include a capacitance forming portion Ac in which the dielectric layer 111 and the internal electrodes 121 and 122 are alternately arranged in the first direction, and cover portions 112 and 113 arranged on both surfaces facing each other in the first direction of the capacitance forming portion Ac. The cover portions 112 and 113 can have a configuration similar to that of the dielectric layer 111, except that they do not include internal electrodes.

[0032] The average thickness tc of the cover parts 112 and 113 is not particularly limited. The average thickness tc of the cover parts 112 and 113 can be, for example, 100 μm or less, 30 μm or less, or 20 μm or less. The average thickness tc of the cover parts 112 and 113 can be, for example, 5 μm or more, 10 μm or more, or 30 μm or more. Here, the average thickness tc of the cover parts 112 and 113 means the respective average thicknesses of the first cover part 112 and the second cover part 113.

[0033] The average thickness tc of the cover parts 112 and 113 can mean the average thickness in the first direction of the cover parts 112 and 113, and can be a value obtained by averaging the thicknesses in the first direction measured at five points equally spaced in the second direction in the cross-sections in the first direction and the second direction of the main body 110.

[0034] The main body 110 can include margin parts 114 and 115 disposed on both surfaces facing the third direction of the capacitance forming part Ac. That is, the margin parts 114 and 115 can mean the regions between the interfaces of the both ends of the internal electrodes 121 and 122 and the main body 110 in the cross-section obtained by cutting the main body 110 in the first direction and the third direction. The margin parts 114 and 115 can have a configuration similar to that of the dielectric layer 111 except for not including the internal electrodes 121 and 122.

[0035] The margin parts 114 and 115 can be formed by applying and firing a conductive paste for the internal electrodes, except where the margin parts are formed on the ceramic green sheet. Alternatively, in order to suppress the step due to the internal electrodes 121 and 122, after exposing the internal electrode patterns on both surfaces facing the third direction of the chip before firing, the margin part forming sheet is attached to both surfaces facing the third direction of the chip before firing and then fired to form the margin parts 114 and 115.

[0036] The average thickness of the margin portions 114 and 115 is not particularly limited. The average thickness of the margin portions 114 and 115 can be, for example, 100 μm or less, 20 μm or less, or 15 μm or less. The average thickness of the margin portions 114 and 115 can be, for example, 5 μm or more, 10 μm or more, or 30 μm or more. Here, the average thickness of the margin portions 114 and 115 means the respective average thicknesses of the first margin portion 114 and the second margin portion 115.

[0037] The average thickness of the margin portions 114 and 115 can mean the average thickness in the third direction of the margin portions 114 and 115, and can be a value obtained by averaging the thicknesses in the third direction measured at five equally spaced points in the first direction from the cross-sections in the first direction and the third direction of the main body 110.

[0038] The external electrodes 130 and 140 can include a first external electrode 130 disposed on the third surface 3 and connected to the first internal electrode 121, and a second external electrode 140 disposed on the fourth surface 4 and connected to the second internal electrode 122. The first external electrode 130 can extend from the third surface 3 onto a part of the first surface, the second surface, the fifth surface, and the sixth surface 1, 2, 5, 6, and the second external electrode 140 can extend from the fourth surface 4 onto a part of the first surface, the second surface, the fifth surface, and the sixth surface 1, 2, 5, 6.

[0039] The type and form of the external electrode are not particularly limited, and it can also have a multilayer structure. For example, the external electrode can include a base electrode layer in contact with the internal electrodes 121 and 122 and a plating layer disposed on the base electrode layer.

[0040] The above base electrode layer can be a sintered electrode containing metal and glass. The metal contained in the above base electrode layer can include Cu, Ni, Pd, Pt, Au, Ag, Pb, and / or an alloy containing the same, etc., but the present invention is not limited thereto. The glass contained in the above base electrode layer can include one or more oxides of Ba, Ca, Zn, Al, B, and Si, but the present invention is not limited thereto.

[0041] The above-mentioned underlayer electrode layer can be formed by dipping the main body 110 into a conductive paste containing metal powder, glass frit, binder, organic solvent, etc., and then firing the conductive paste at a temperature of 500°C to 900°C.

[0042] On the other hand, the above-mentioned underlayer electrode layer can be composed of only the first layer containing metal and glass, but the present invention is not limited thereto, and the above-mentioned underlayer electrode layer can have a multilayer structure. For example, the above-mentioned underlayer electrode layer can include a first layer containing metal and glass and a second layer disposed on the first layer and containing metal and resin.

[0043] The metal contained in the above-mentioned second layer can include one or more of spherical particles and flaky particles. Here, the spherical particles can include forms that are not completely spherical. For example, forms with a length ratio of the major axis to the minor axis (major axis / minor axis) of 1.45 or less can be included. The flaky particles mean powders having a flat and elongated form, and are not particularly limited. For example, the length ratio of the major axis to the minor axis (major axis / minor axis) can be 1.95 or more.

[0044] The metal contained in the above-mentioned second layer can include, for example, Cu, Ni, Pd, Pt, Au, Ag, Pb, Sn, and / or an alloy containing these. The resin contained in the above-mentioned second layer can include, for example, one or more of epoxy resin, acrylic resin, and ethyl cellulose.

[0045] When the above-mentioned underlayer electrode layer includes a first layer containing metal and glass and a second layer containing metal and resin, the second layer can be formed by applying a conductive resin composition containing metal powder, resin, binder, organic solvent, etc. on the first layer and then performing a curing heat treatment at a temperature of 250°C to 550°C.

[0046] The above plating layer can improve the mounting characteristics. The above plating layer can include, for example, Ni, Sn, Pd, and / or an alloy containing the same, and can also be formed of a plurality of layers. The plating layer can be, for example, a Ni plating layer or a Sn plating layer, or can be in a form in which a Ni plating layer and a Sn plating layer are sequentially formed. Further, the above plating layer can also include a plurality of Ni plating layers and / or a plurality of Sn plating layers.

[0047] In one embodiment, the multilayer electronic component 100 can include connection electrodes 12 and 13 disposed on the end sides of the internal electrodes 121 and 122. The first connection electrode 12 is disposed on the end side of the first internal electrode 121 and can connect the first internal electrode 121 and the first external electrode 130. The second connection electrode 13 is disposed on the end side of the second internal electrode 122 and can connect the second internal electrode 122 and the second external electrode 140. The connection electrodes 12 and 13 can contact the internal electrodes 121 and 122 inside the main body 110 and can contact the external electrodes 130 and 140 outside the main body 110.

[0048] The connection electrodes 12 and 13 can include, for example, one or more of Ni, Cu, and Pd. The connection electrodes 12 and 13 can be formed by an electrolytic plating method and / or an electroless plating method, but the present invention is not limited thereto.

[0049] In the drawings, a structure in which the multilayer electronic component 100 has two external electrodes 131 and 132 is described, but the present invention is not limited thereto, and the number and shape of the external electrodes 131 and 132 can vary according to the form of the internal electrodes 121 and 122 and other purposes.

[0050] On the other hand, the size of the multilayer electronic component 100 is not particularly limited. For example, the length of the multilayer electronic component 100 in the second direction can be 0.15 mm to 3.50 mm, the width of the multilayer electronic component 100 in the third direction can be 0.05 mm to 1.65 mm, and the thickness of the multilayer electronic component 100 in the first direction can be 0.05 mm to 2.0 mm.

[0051] The dielectric layer 111 can include a secondary phase 11 containing Zr and Y. Referring to FIG. 4, at least a part of the secondary phase 11a among the secondary phases 11 contained in the dielectric layer 111 is in contact with the internal electrodes 121 and 122, and the remaining part of the secondary phase 11b can be arranged separated from the internal electrodes 121 and 122.

[0052] In this specification, the "secondary-phase" can mean particles or segregation having a composition or crystal lattice different from that of perovskite-based (ABO3) dielectric particles, and can mean an aggregate of components not dissolved in the dielectric crystal grains, but is not particularly limited thereto.

[0053] 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 CSZT-based dielectric material. That is, the secondary phase 11 of the multilayer electronic component 100 according to an embodiment of the present invention can mean an aggregate of elements containing Zr and Y that are not dissolved or substituted in the crystal lattice structure of the dielectric crystal grains that are the main component of the CSZT system.

[0054] According to an embodiment of the present invention, among the secondary phases 11 contained in the dielectric layer 111, the ratio of the number of the secondary phases 11a in contact with the internal electrodes 121 and 122 can be 70% or more. The secondary phase 11 containing Zr and Y is a kind of low-resistance phase. When the secondary phase 11 is arranged separated from the internal electrodes 121 and 122, the probability of forming a conductive path that electrically connects the adjacent internal electrodes 121 and 122 increases, and as a result, there is a risk of reducing the insulation resistance of the multilayer electronic component 100 or causing a short-circuit defect.

[0055] Therefore, among the secondary phases 11 contained in the dielectric layer 111, the ratio of the number of the secondary phases 11a in contact with the internal electrodes 121 and 122 is preferably 70% or more, thereby improving the high-temperature reliability and moisture resistance reliability of the multilayer electronic component 100 and preventing the insulation resistance of the multilayer electronic component 100 from decreasing.

[0056] On the other hand, among the secondary phases 11 included in the dielectric layer 111, the upper limit of the percentage of the number of the secondary phases 11a in contact with the internal electrodes 121 and 122 is not particularly limited, but in order to prevent other characteristics from deteriorating, the percentage can be 95% or less.

[0057] More specifically, regarding the method for measuring the above percentage, when the cross-sections in the first and second directions of the capacitance forming portion Ac cut at the center in the third direction of the main body 110 are mapped for Zr and Y in the EDS mode of SEM, TEM, or STEM, the collective regions of Zr and Y observed in the dielectric layer 111 can be defined as the secondary phase 11. At this time, the secondary phase having a length of 0.05 μm or more in contact with the internal electrodes 121 and 122 among the secondary phases 11 can be defined as the secondary phase 11a in contact with the internal electrodes 121 and 122. At this time, the ratio of the number of the secondary phases 11a in contact with the internal electrodes 121 and 122 to the total number of the secondary phases 11 observed in the above cross-section can be defined as the above percentage.

[0058] On the other hand, in all regions of the capacitance forming portion Ac, it is not necessary to satisfy that the above percentage is 70% or more. If the percentage of the number of the secondary phases 11a in contact with the internal electrodes 121 and 122 among the secondary phases 11 existing in at least one 10 μm × 10 μm region of the capacitance forming portion Ac is 70% or more, the reliability and insulation resistance of the multilayer electronic component 100 can be improved. That is, in one embodiment, the capacitance forming portion Ac can include a 10 μm × 10 μm region where the above percentage is 70% or more. The above 10 μm × 10 μm region can be located, for example, at the center of the cross-sections in the first and second directions cut at the center in the third direction of the main body 110 (for example, the P region in FIG. 2). However, it is more preferable that the percentage of the number of the secondary phases 11a in contact with the internal electrodes 121 and 122 among the secondary phases 11 existing in any 10 μm × 10 μm region within the capacitance forming portion Ac is 70% or more.

[0059] In one embodiment, the number of the secondary phases 11a in contact with the internal electrodes 121 and 122 in the 10 μm × 10 μm region can be five or more. If the number of the secondary phases 11a in contact with the internal electrodes 121 and 122 in the 10 μm × 10 μm region is less than five, the effect of improving the reliability of the present invention may be slight. The upper limit of the number of the secondary phases 11a in contact with the internal electrodes 121 and 122 in the 10 μm × 10 μm region is not particularly limited, but can be 100 or less in order to prevent other characteristics from deteriorating.

[0060] In one embodiment, the ratio of the area occupied by the secondary phase 11 to the total area occupied by the dielectric layer 111 in the 10 μm × 10 μm region can be 5% or less. When the ratio of the area occupied by the secondary phase 11 to the total area occupied by the dielectric layer 111 in the 10 μm × 10 μm region exceeds 5%, secondary effects such as a decrease in the insulation resistance of the multilayer electronic component 100 may occur. On the other hand, the lower limit of the ratio of the area occupied by the secondary phase 11 to the total area occupied by the dielectric layer 111 in the 10 μm × 10 μm region is not particularly limited, but can exceed 0% or be 1.5% or more.

[0061] Here, the area of the secondary phase 11 can be measured by applying the program filter function of "Image Pro Plus", which is an image analysis program, to remove noise other than the secondary phase 11 containing Zr and Y, but is not particularly limited thereto.

[0062] In one embodiment, the cover portions 112 and 113 can contain the secondary phase containing Zr and Y. By also including the secondary phase in the cover portions 112 and 113, the high-temperature reliability and moisture resistance reliability of the multilayer electronic component 100 can be more effectively improved.

[0063] In one embodiment, the ratio of the area occupied by the secondary phase in the cover portions 112 and 113 can be higher than the ratio of the area occupied by the secondary phase in the dielectric layer 111. Since the cover portions 112 and 113 do not include the internal electrodes 121 and 122 unlike the capacitance forming portion Ac, the probability of occurrence of the problem of conductive path formation due to the above-described secondary phase is relatively low. Therefore, when the ratio of the area occupied by the secondary phase in the cover portions 112 and 113 is higher than the ratio of the area occupied by the secondary phase in the dielectric layer 111, the high-temperature reliability and moisture resistance reliability of the multilayer electronic component 100 can be effectively improved without significantly affecting the insulation resistance of the multilayer electronic component 100.

[0064] On the other hand, the secondary phase 11 containing Zr and Y can be different from the composition of the CSZT-based dielectric crystal grains. For example, when the atomic percentage of Zr contained in the secondary phase 11 is S Zr , the atomic percentage of Y contained in the secondary phase 11 is S Y , the atomic percentage of Zr contained in the remaining region of the dielectric layer 111 excluding the secondary phase 11 is R Zr , and the atomic percentage of Y contained in the remaining region of the dielectric layer 111 excluding the secondary phase 11 is R Y , then S Zr >R Zr , and S Y >R Y can be satisfied.

[0065] Here, S Zr and S Y can mean the average value of the atomic percentages of the respective elements measured at three or more points of the same secondary phase 11, and R Zr and R Y can mean the average value of the atomic percentages of the respective elements measured at five or more points of the same dielectric crystal grain, but is not particularly limited thereto.

[0066] In one embodiment, the above S Zr can be 0.1 at% or more and 50 at% or less, and the above S Y can be 0.1 at% or more and 10 at% or less. 0.1 at% ≦ S Zr≤50 at% and 0.1 at% ≤ S Y By satisfying ≤10 at%, the reliability and the effect of improving the insulation resistance of the present invention can be made more remarkable.

[0067] On the other hand, as an example of a more specific method for measuring the content of each element contained in the remaining region excluding the secondary phase 11 among the secondary phase 11 and the dielectric layer 111, the components of each region can be analyzed using SEM-EDS, TEM-EDS, or STEM-EDS. First, a thin analysis sample is prepared using a focused ion beam (FIB) equipment in a region including the dielectric layer in the cross-section of the fired body. Then, the damaged layer on the surface of the thinned sample is removed using Ar ion milling, and thereafter, qualitative / quantitative analysis is performed by mapping each component in the image obtained using STEM-EDS or the like. In this case, the qualitative / quantitative analysis graph of each component can be represented by converting it into the mass fraction (wt%), atomic percentage (at%), or molar fraction (mol%) of each element.

[0068] On the other hand, the average diameter of the plurality of dielectric crystallites contained in the dielectric layer 111 can be 300 nm or more and 500 nm or less. This can correspond to the result of firing the main component powder having a size of 70 nm to 150 nm, but is not particularly limited thereto. By satisfying that the average diameter of the plurality of dielectric crystallites contained in the dielectric layer 111 is 300 nm or more and 500 nm or less, the high-temperature and moisture-resistant reliability and the insulation resistance characteristics can be further improved. In one embodiment, the standard deviation of the diameters of the plurality of dielectric crystallites contained in the dielectric layer 111 can be 200 nm or less. By satisfying that the standard deviation of the diameters of the plurality of dielectric crystallites contained in the dielectric layer 111 is 200 nm or less, the dispersion of the diameters of the dielectric crystallites is improved, so that the multilayer electronic component 100 can satisfy 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). For example, the maximum value among the diameters of the plurality of dielectric crystallites contained in the dielectric layer 111 can be 1000 nm or less.

[0069] The average diameter and standard deviation of the plurality of dielectric crystal grains included in the dielectric layer 111 can correspond to, for example, the average and standard deviation of the diameters of the plurality of dielectric crystal grains included in the dielectric layer 111 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. Here, the diameter of the dielectric crystal grain can mean the size of any straight line passing through the center of the dielectric crystal grain, and more specifically, it can mean the size of the straight line in the first direction passing through the center of the dielectric crystal grain, but it is not particularly limited thereto.

[0070] On the other hand, as described above, the dielectric layer 111 can include a main component having a perovskite structure represented by the general formula ABO3, for example, a CSZT-based main component and a sub-component, and more specifically, can further include the following first to fourth sub-components.

[0071] a) First sub-component The dielectric layer 111 can further include a first sub-component element, and the first sub-component element can be a rare earth element. The rare earth element can be one or more of Y, Dy, Tb, Gd, Ce, Nd, La, and Yb, and more preferably, the first sub-component element can be Y.

[0072] The rare earth element, which is the first sub-component element, can play a role in improving the high-temperature accelerated life and can play a role in improving the reliability. The first sub-component can be one or more of oxides and carbonates of rare earth elements and can be added together to the main component raw material before firing.

[0073] At this time, the number of moles of the first sub-component element with respect to 100 moles of Zr contained in the dielectric crystal grains of the dielectric layer 111 can be 0.05 moles or more and 3.5 moles or less. When the number of moles of the first sub-component element with respect to 100 moles of Zr contained in the dielectric crystal grains of the dielectric layer 111 is less than 0.05 moles, the high-temperature accelerated life may decrease. When the number of moles of the first sub-component element with respect to 100 moles of Zr contained in the dielectric crystal grains of the dielectric layer 111 exceeds 3.5 moles, the insulation resistance (IR) may decrease due to the n-type semiconductor conversion of the dielectric, or the high-temperature accelerated life may decrease.

[0074] b) The second sub-component The dielectric layer 111 can further contain a second sub-component element, and the second sub-component element can be a variable-valence acceptor element, and the variable-valence acceptor element can be one or more of Mn, V, Cr, Fe, Co, Ni, Cu, Co, and Zn.

[0075] The second sub-component can be one or more of oxides or carbonates of the variable-valence acceptor element, and can be added together to the main component raw material before firing. The variable-valence acceptor element that is the second sub-component element can play a role in improving the firing temperature reduction, dielectric properties, and high-temperature accelerated life characteristics.

[0076] At this time, the number of moles of the second sub-component element with respect to 100 moles of Zr contained in the dielectric crystal grains of the dielectric layer 111 can be 0.1 moles or more and 0.8 moles or less. When a plurality of second sub-component elements are added, the total content of these can be defined as the number of moles of the second sub-component element.

[0077] When the content of the second sub-component element with respect to 100 moles of Zr contained in the dielectric crystal grains of the dielectric layer 111 is less than 0.1 moles, the insulation resistance may decrease. When the content of the second sub-component element with respect to 100 moles of Zr contained in the dielectric crystal grains of the dielectric layer 111 exceeds 0.8 moles, the DC-bias change rate may decrease.

[0078] c) The third sub-component The dielectric layer 111 can further contain a third sub-component element, and the third sub-component element can be Mg.

[0079] The third sub-component can be one or more of Mg oxides and carbonates, and can be added together to the main component raw material before firing. Mg, which is the third sub-component element, can impart reduction resistance and play a role in increasing the RC (Reliability Class) value. Here, the RC value can mean reliability depending on temperature, reliability at high temperatures, reliability at high voltages, life evaluation, etc.

[0080] At this time, the number of moles of the third sub-component element with respect to 100 moles of Zr contained in the dielectric crystal grains of the dielectric layer 111 can be more than 0 moles and 1 mole or less.

[0081] When the third sub-component element is not added to the dielectric layer 111, for example, when the content of the third sub-component element with respect to 100 moles of Zr contained in the dielectric crystal grains of the dielectric layer 111 is 0 moles, there is a risk of reduced reliability. When the content of the third sub-component element with respect to 100 moles of Zr contained in the dielectric crystal grains of the dielectric layer 111 exceeds 1 mole, there is a risk of not meeting the X7R temperature characteristics.

[0082] d) The fourth sub-component The dielectric layer 111 can further contain a fourth sub-component element, and the fourth sub-component element can be Si.

[0083] The fourth sub-component can be at least one of Si oxides, Si carbonates, and glass containing Si, and can be added together to the main component raw material before firing. Si, which is the fourth sub-component element, can play a role in improving insulation resistance or high-temperature accelerated life.

[0084] At this time, the number of moles of the fourth sub-component element with respect to 100 moles of Zr contained in the dielectric crystal grains of the dielectric layer 111 can be 0.1 mole or more and 2.0 moles or less.

[0085] When the number of moles of the fourth sub-component element with respect to 100 moles of Zr contained in the dielectric crystal grains of the dielectric layer 111 is less than 0.1 mole, the insulation resistance 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 Zr contained in the dielectric crystal grains of the dielectric layer 111 exceeds 2.0 moles, the room-temperature dielectric constant may decrease.

[0086] FIG. 6 is a cross-sectional view schematically showing a multilayer electronic component 100' according to another embodiment of the present invention, and is a drawing corresponding to FIG. 2.

[0087] Hereinafter, with reference to FIG. 6, a multilayer electronic component 100' according to another embodiment of the present invention will be described. For the configurations that are the same as or similar to the configuration of the multilayer electronic component 100 described in FIG. 2, the same or similar reference numerals will be used, and the redundant description will be omitted.

[0088] The main body 110 of the multilayer electronic component 100' according to an embodiment of the present invention may include a plurality of capacitance forming portions Ac1, Ac2 in which a dielectric layer 111a and internal electrodes 121, 122 are alternately arranged in a first direction, and a buffer layer 111b arranged between adjacent capacitance forming portions Ac1, Ac2. The buffer layer 111b can be thicker than the dielectric layer 111a.

[0089] The buffer layer 111b can basically play a role in improving the mechanical strength of the multilayer electronic component 100' or improving the withstand voltage characteristics of the multilayer electronic component 100'. It can have a dielectric composition similar to that of the dielectric layer 111a. That is, the buffer layer 111b can contain the secondary phase containing the above-mentioned Zr and Y. Thereby, the reliability improvement effect of the present invention can be made more remarkable.

[0090] In FIG. 6, a structure in which there are two capacitance forming portions Ac1, Ac2 and one buffer layer 111b is shown, but the present invention is not limited thereto. The capacitance forming portions Ac1, Ac2 can be three or more, and the buffer layer 111b can be two or more.

[0091] (Experimental example) Table 1 below shows the size of the main component powder, the firing temperature, and the contents of the first to fourth sub-component elements. The unit of the size of the main component powder is nm, the unit of the firing temperature is °C, and the first to fourth sub-components correspond to the number of moles of the first to fourth sub-component elements. For example, in sample number 1, 0.05 mol of the first sub-component Y2O3 corresponds to 0.05 mol of Y, 0.32 mol of the second sub-component MnO2 corresponds to 0.32 mol of Mn, 0.32 mol of the third sub-component MgCO3 corresponds to 0.32 mol of Mg, and 0.32 mol of the fourth sub-component SiO2 corresponds to 0.32 mol of Si.

[0092] As the main component powder, CSZT-based powder with an average particle size of about 150 nm was used. Using zirconia beads as the mixing / dispersing media, the raw material powder containing sub-component elements corresponding to the composition specified in Table 1 and the main component CSZT-based powder were mixed with an ethanol / toluene solvent and a dispersant and milled for 7 hours, and after mixing a binder, it was further milled for 1 hour to provide a slurry. The slurry thus produced was used to produce a ceramic green sheet with a thickness of 0.1 μm to 3 μm using a sheet manufacturing molding machine. Thereafter, a nickel (Ni) internal electrode pattern was printed on the ceramic green sheet. The cover part was produced by laminating 20 or more layers of cover part sheets, and the ceramic laminate was formed by laminating and pressing the ceramic green sheet printed with a total of 20 or more internal electrode patterns, and then cut into chips of size 0201 (length × width: 2.0 mm × 1.0 mm) using a cutting machine. After the produced chips were plastically processed, they were fired under the conditions of maintaining the temperature at 1300 °C or lower for 10 hours or less in a reducing atmosphere of 10% H2 or more / 30% N2 or more (H2 / N2 atmosphere), and then re-oxidized in a N2 atmosphere at 1000 °C or lower for 10 hours. An external electrode was completed through a dipping process and electrode firing with Cu paste on the fired chips to provide sample chips.

[0093] [Table 1]

[0094] In Table 2 below, the area ratio (%) corresponds to the ratio of the area of the secondary phase existing within the 10 μm × 10 μm region to the total area of the dielectric layer existing within the 10 μm × 10 μm region when observing a 10 μm × 10 μm region of the capacitance forming portion located at the center of the cross-section in the first and second directions, cut at the center in the third direction of the main body.

[0095] IR (Insulation Resistance) is described by taking 10 sample chips each and measuring the insulation resistance value at room temperature. When the insulation resistance of all sample chips is 10 8 Ω or more, it is excellent (○); when it is 10 5 Ω or more and less than 10 8 Ω, it is normal (△); when it is less than 10 5 Ω, it is evaluated as defective (×).

[0096] The reliability evaluation was performed by accelerated life evaluation (HALT). For 40 sample chips per sample number, a voltage of 100 V was applied at 125 °C or higher, and the time until failure occurred was measured to calculate the mean time to failure (MTTF). After that, when the MTTF of all sample chips was 50,000 hours or more, it was evaluated as excellent (○); when it was 10,000 hours or more and less than 50,000 hours, it was normal (△); when it was less than 10,000 hours, it was evaluated as defective (×).

[0097]

Table 2

[0098] Referring to sample numbers 1 to 10 in Table 2 above, it can be confirmed that when the ratio of the area occupied by the secondary phase to the total area occupied by the dielectric layer in the 10 μm × 10 μm region is 5% or less, the insulation resistance of the sample chip is excellent. On the other hand, referring to sample numbers 11 and 12, it can be confirmed that when the ratio of the area occupied by the secondary phase exceeds 5%, the insulation resistance decreases.

[0099] On the one hand, referring to Sample Numbers 1 to 10, it can be confirmed that the reliability evaluation is good. In particular, when the ratio of the area occupied by the secondary phase is 1.5% or more, it can be confirmed that the reliability of the sample chip is excellent.

[0100] On the other hand, for Sample Number 12, all of the insulation resistance and reliability evaluation were poor. Also, for Sample Number 11, the results of both the insulation resistance and reliability evaluation were ordinary. It can be confirmed that the result of the insulation resistance evaluation was good, and it deteriorated compared to Sample Numbers 1 and 2 where only the result of the reliability evaluation was ordinary.

[0101] The present invention is not limited by the above-described embodiments and the accompanying drawings, but is limited by the appended claims. Therefore, within the scope not departing from the technical idea of the present invention described in the claims, various forms of substitution, modification, and change are possible by those having ordinary knowledge in the technical field, and it can be said that these also belong to the scope of the present invention.

[0102] Also, the expression "one embodiment" does not mean the same embodiment, but is provided to emphasize and explain each different unique feature. However, it does not exclude that the above-presented one embodiment is implemented in combination with the features of another one embodiment. 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.

[0103] Furthermore, expressions such as first, second, etc. are used to distinguish one component from another component, and do not limit the order and / or importance, etc. of the corresponding components. In some cases, without departing from the scope of the rights, the first component can also be named the second component, and similarly, the second component can be named the first component.

Explanation of Reference Numerals

[0104] 100 Multilayer Electronic Component 110 body 111 dielectric layer 112, 113 cover part 114, 115 margin part 121, 122 internal electrode 130, 140 external electrode 11 secondary phase 12, 13 connecting electrode

Claims

1. A main body including a dielectric layer and internal electrodes alternately arranged with the dielectric layer, and an external electrode disposed on the main body, wherein the dielectric layer includes a secondary phase containing Zr and Y, A multilayer electronic component, wherein a proportion of the number of secondary phases in contact with the internal electrode among the secondary phases included in the dielectric layer is 70% or more.

2. The main body includes a capacitance forming portion in which the dielectric layer and the internal electrodes are alternately arranged in a first direction, and cover portions disposed on both surfaces of the capacitance forming portion facing each other in the first direction, The capacitance forming portion includes a 10 μm × 10 μm region in which the proportion is 70% or more. The multilayer electronic component according to claim 1.

3. In the 10 μm × 10 μm region, the number of secondary phases in contact with the internal electrode is 5 or more. The multilayer electronic component according to claim 2.

4. In the 10 μm × 10 μm region, a proportion of an area occupied by the secondary phase in an entire area occupied by the dielectric layer is 5% or less. The multilayer electronic component according to claim 2.

5. Let the atomic percentage of Zr contained in the secondary phase be S Ｚｒ and the atomic percentage of Y contained in the secondary phase be S Ｙ Let the atomic percentage of Zr contained in the remaining region of the dielectric layer excluding the secondary phase be R Ｚｒ and the atomic percentage of Y contained in the remaining region of the dielectric layer excluding the secondary phase be R Ｙ When this is the case, S Ｚｒ > R Ｚｒ and S Ｙ > R Ｙ The multilayer electronic component according to claim 1, which satisfies these conditions.

6. Let the atomic percentage of Zr contained in the secondary phase be S Ｚｒ and the atomic percentage of Y contained in the secondary phase be S Ｙ When doing so, the S Ｚｒ is 0.1 at% or more and 50 at% or less, and the S Ｙ is 0.1 at% or more and 10 at% or less. The multilayer electronic component according to claim 1

7. The dielectric layer contains a main component having a perovskite structure represented by the general formula ABO ３ and The A-site element includes one or more of Ca and Sr, The B-site element includes Zr. The multilayer electronic component according to claim 1.

8. The dielectric layer further includes a first sub-component element, The first sub-component element is a rare earth element, The rare earth element is one or more of Y, Dy, Tb, Gd, Ce, Nd, La, and Yb. The multilayer electronic component according to claim 7.

9. The dielectric layer further includes a second sub-component element, The second sub-component element is one or more of Mn, V, Cr, Fe, Co, Ni, Cu, Co, and Zn. The multilayer electronic component according to claim 7.

10. The dielectric layer further includes a third sub-component element, The third sub-component element is Mg. The multilayer electronic component according to claim 7.

11. The dielectric layer further includes a fourth sub-component element, The fourth sub-component element is Si. The multilayer electronic component according to claim 7.

12. The main body includes a capacitance forming portion in which the dielectric layer and the internal electrodes are alternately arranged in a first direction, and cover portions disposed on both surfaces of the capacitance forming portion facing each other in the first direction, The cover portion includes the secondary phase. The multilayer electronic component according to claim 1.

13. The laminated electronic component according to claim 12, wherein the ratio of the area occupied by the secondary phase in the cover portion is higher than the ratio of the area occupied by the secondary phase in the dielectric layer.

14. The main body includes a plurality of capacitance forming portions in which the dielectric layer and the internal electrodes are alternately arranged in a first direction, and a buffer layer arranged between adjacent capacitance forming portions. The laminated electronic component according to claim 1, wherein the buffer layer includes the secondary phase and is thicker than the dielectric layer.

15. The dielectric layer includes a plurality of dielectric crystallites. The laminated electronic component according to claim 1, wherein an average diameter of the plurality of dielectric crystallites is 300 nm to 500 nm.

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