Multilayer electronic component

Abstract

The present disclosure provides a multilayer electronic component including: a main body including a capacitance forming portion including a dielectric layer and internal electrodes alternately disposed with the dielectric layer in a first direction, and a cover portion covering the dielectric layer, the covering part is arranged on the upper surface and the lower surface of the capacitance forming part in the first direction; and an external electrode disposed on the main body, and the covering portion may include titanium (Ti), gallium (Ga), and phosphorus (P), and a molar amount of the gallium (Ga) included in the covering portion may be 0.3 moles or more and 6.0 moles or less with respect to 100 moles of titanium (Ti).

Description

[0001] This application claims the benefit of priority from Korean Patent Application No. 10-2023-0158382 filed on November 15, 2023 in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference. Technical Field

[0002] The present disclosure relates to a multi-layer electronic assembly. Background Art

[0003] Multilayer ceramic capacitors (MLCC, a type of multilayer electronic component) are chip capacitors mounted on printed circuit boards of various types of electronic products such as image display devices (such as liquid crystal displays (LCDs) and plasma display panels (PDPs)), computers, smart phones, and mobile phones, and are used to charge or discharge them.

[0004] Multilayer ceramic capacitors can be used as components in various electronic devices because they have a small size, ensure high capacitance, and are easy to install. As various electronic devices (such as computers and mobile devices) are miniaturized and achieve high output power, the demand for miniaturization and high capacitance of multilayer ceramic capacitors is also increasing.

[0005] As miniaturization and the achievement of higher capacitance advance, the need to protect the capacitance forming area increases, and this has been improved by increasing the edge area surrounding the capacitance forming area. However, due to the continuous change in structural design to achieve miniaturization and high capacitance, the capacitance forming area may increase and the edge area protecting the capacitance forming area may decrease, so there may be a risk that the moisture resistance reliability and strength of the multilayer ceramic capacitor may be reduced. Summary of the invention

[0006] An aspect of the present disclosure is to provide a multilayer electronic component having excellent heat resistance in a high temperature and high humidity environment by improving the compactness of a cover.

[0007] An aspect of the present disclosure is to provide a multilayer electronic component having improved moisture resistance and reliability.

[0008] However, aspects of the present disclosure are not limited to the above and may be more easily understood in describing specific example embodiments of the present disclosure.

[0009] According to some example embodiments of the present disclosure, a multilayer electronic component may include: a main body including a capacitor forming portion and a covering portion, the capacitor forming portion including a dielectric layer and internal electrodes alternately arranged with the dielectric layer in a first direction, the covering portion being arranged on two surfaces of the capacitor forming portion in the first direction; and an external electrode arranged on the main body, and the covering portion may include titanium (Ti), gallium (Ga) and phosphorus (P), and a molar amount of gallium (Ga) included in the covering portion relative to 100 moles of titanium (Ti) may be greater than or equal to 0.3 moles and less than or equal to 6.0 moles.

[0010] According to another example embodiment of the present disclosure, a multilayer electronic component may include: a main body, including a capacitor forming portion and a covering portion, the capacitor forming portion including a dielectric layer and internal electrodes alternately arranged with the dielectric layer in a first direction, the covering portion being arranged on two surfaces of the capacitor forming portion in the first direction; and an external electrode, arranged on the main body, and the covering portion may include titanium (Ti), gallium (Ga) and phosphorus (P), and the molar amount of phosphorus (P) included in the covering portion relative to 100 moles of titanium (Ti) may be greater than 0 mole and less than or equal to 5.0 moles.

[0011] One of the various effects of the present disclosure may be to improve the heat resistance of a multilayer electronic component in a high-temperature and high-humidity environment by improving the compactness of a cover portion.

[0012] One of various effects of the present disclosure may be to improve the moisture resistance reliability of a multilayer electronic component.

[0013] However, the advantages and effects of the present application are not limited to the foregoing and may be more easily understood in the course of describing specific exemplary embodiments of the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The above and other aspects, features and advantages of the present disclosure will be more clearly understood through the following detailed description in conjunction with the accompanying drawings, in which:

[0015] Figure 1 is a perspective view schematically illustrating a multilayer electronic component according to an example embodiment of the present disclosure;

[0016] Figure 2 is an exploded perspective view schematically showing a stacked structure of the main body;

[0017] Figure 3 It is along Figure 1 A schematic cross-sectional view taken along line II' of ;

[0018] Figure 4 It is along Figure 1 A schematic cross-sectional view taken along line II-II';

[0019] Figure 5A is an image of a cross section of the cover portion of the comparative example captured in the HAADF mode of a transmission electron microscope (TEM), Figure 5B is through Figure 5A An image obtained by performing EDS analysis in a region to map the aluminum (Al) element, and Figure 5C is through Figure 5A An image obtained by performing EDS analysis in an area to map the silicon (Si) element;

[0020] Fig. 6A is an image of a cross section of the cover portion of the inventive example captured in the HAADF mode of a transmission electron microscope (TEM), Figure 6B is through Fig. 6A An image obtained by performing EDS analysis in an area to map the aluminum (Al) element, Figure 6C is through Fig. 6A An image obtained by performing EDS analysis in a region to map the silicon (Si) element, and Fig.6D is through Fig. 6A An image obtained by performing EDS analysis in a region of the image to map the gallium (Ga) element;

[0021] Figure 7 This is an image of phosphorus (P) element mapped by capturing a cross section of the cover portion of the inventive example using a transmission electron microscope (TEM) and then performing EDS analysis;

[0022] Fig. 8A is a humidity resistance reliability evaluation diagram of a comparative example. Figure 8B is a moisture resistance reliability evaluation diagram of the invention example; and

[0023] Fig.9A This is a reliability (MTTF) evaluation chart of the comparative example under harsh conditions. Fig. 9B This is a reliability (MTTF) evaluation diagram of the invention example under harsh conditions. DETAILED DESCRIPTION

[0024] Hereinafter, example embodiments of the present disclosure will be described with reference to the accompanying drawings. However, example embodiments of the present disclosure may be illustrated in many different forms and should not be construed as being limited to the specific embodiments set forth herein. The example embodiments disclosed herein are provided to enable those skilled in the art to better explain the present disclosure. Therefore, in the accompanying drawings, the shapes and sizes of the elements may be exaggerated for clarity, and the same or similar reference numerals will always be used to indicate the same or similar elements.

[0025] In addition, in order to clearly describe the present disclosure in the drawings, the contents irrelevant to the description are omitted, and since the size (e.g., thickness) of each component shown in the drawings is arbitrarily shown for the convenience of description, the present disclosure is not limited thereto. In addition, the same reference numerals are used to describe components having the same functions within the same conceptual scope. Throughout the specification, when a part is described as "including" or "comprising" a component, unless otherwise specified, this indicates that other components are not excluded and other components may be further included.

[0026] In the drawings, a first direction may be defined as a thickness direction (T direction), a second direction may be defined as a length direction (L direction), and a third direction may be defined as a width direction (W direction).

[0027] Multilayer electronic components

[0028] Figure 1 is a perspective view schematically illustrating a multilayer electronic component according to an example embodiment of the present disclosure.

[0029] Figure 2 It is an exploded perspective view schematically showing the stacking structure of the main body.

[0030] Figure 3 It is along Figure 1 Schematic cross-sectional view taken along line II'.

[0031] Figure 4 It is along Figure 1 Schematic cross-sectional view taken along line II-II'.

[0032] In the following, reference will be made to Figures 1 to 4 A multilayer electronic component according to an example embodiment of the present disclosure is described in detail. However, although a multilayer ceramic capacitor will be described as an example of a multilayer electronic component, the multilayer electronic component of the present disclosure can also be applied to various electronic products (such as inductors, piezoelectric elements, varistors, or thermistors) using a dielectric composition.

[0033] According to some example embodiments of the present disclosure, a multilayer electronic component 100 may include: a main body 110 including a capacitor forming portion Ac and covering portions 112 and 113, the capacitor forming portion Ac including a dielectric layer 111 and internal electrodes 121 and 122 alternately arranged with the dielectric layer 111 in a first direction, the covering portions 112 and 113 being arranged on both surfaces of the capacitor forming portion Ac in the first direction; and external electrodes 131 and 132 arranged on the main body 110, and the covering portions 112 and 113 may include titanium (Ti), gallium (Ga) and phosphorus (P), and the molar amount of gallium (Ga) included in the covering portions 112 and 113 relative to 100 moles of titanium (Ti) may be greater than or equal to 0.3 moles and less than or equal to 6.0 moles.

[0034] A multilayer electronic component 100 according to another example embodiment of the present disclosure may include: a main body 110, including a capacitor forming portion Ac and covering portions 112 and 113, the capacitor forming portion Ac including a dielectric layer 111 and internal electrodes 121 and 122 alternately arranged with the dielectric layer 111 in a first direction, the covering portions 112 and 113 being arranged on two surfaces of the capacitor forming portion Ac in the first direction; and external electrodes 131 and 132, which are arranged on the main body 110, and the covering portions 112 and 113 may include titanium (Ti), gallium (Ga) and phosphorus (P), and the molar amount of phosphorus (P) included in the covering portions 112 and 113 relative to 100 moles of titanium (Ti) may be greater than 0 mole and less than or equal to 5.0 moles.

[0035] Hereinafter, various embodiments of the present disclosure will be described in more detail.

[0036] The body 110 may include dielectric layers 111 and internal electrodes 121 and 122 that are alternately stacked.

[0037] More specifically, the body 110 may include a capacitor forming portion Ac disposed inside the body 110 and including first and second internal electrodes 121 and 122 alternately arranged to face each other with a dielectric layer 111 interposed therebetween to form a capacitor.

[0038] The specific shape of the main body 110 is not particularly limited, but Figure 1 As shown, the body 110 may have a hexahedral shape or a shape similar thereto. Since ceramic powder particles included in the body 110 shrink during a sintering process, the body 110 may not have a hexahedral shape with completely straight lines but may have a substantially hexahedral shape.

[0039] The main body 110 may 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 surface 1, the second surface 2, the third surface 3, and the fourth surface 4 and face each other in a third direction.

[0040] In a state where a plurality of dielectric layers 111 included in the main body 110 are sintered, adjacent dielectric layers 111 may be integrated with each other such that it is difficult to identify the boundary therebetween without using a scanning electron microscope (SEM).

[0041] There is no limitation on the material included in the dielectric layer 111 as long as sufficient electrostatic capacitance can be obtained thereby. Generally, the dielectric layer 111 may include a perovskite (ABO3)-based material, such as a barium titanate-based material, a lead composite perovskite-based material, or a strontium titanate-based material. The barium titanate-based material may include BaTiO3-based ceramic particles, and examples of the BaTiO3-based ceramic particles may include BaTiO3 or (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).

[0042] In addition, for the purpose of the present disclosure, various ceramic additives, organic solvents, binders, dispersants, etc. may be added to particles such as barium titanate (BaTiO3) as the material included in the dielectric layer 111.

[0043] In addition, the dielectric layer 111 may be formed by using a dielectric material such as barium titanate (BaTiO3), and thus may include a dielectric microstructure after sintering. The dielectric microstructure may include a plurality of grains, grain boundaries provided between adjacent grains, and triple junctions provided at points where three or more grain boundaries contact each other, and the number of each of the grains, grain boundaries, and triple junctions included in the dielectric microstructure may be more than one.

[0044] In the present disclosure, in order to distinguish the dielectric layers included in the capacitor forming portion Ac, the covering portions 112 and 113, and the side edge portions 114 and 115 (to be described below), the dielectric layer 111 included in the capacitor forming portion Ac may be defined as a first dielectric layer 111, the dielectric layer included in the covering portions 112 and 113 may be defined as a second dielectric layer, and the dielectric layer included in the side edge portions 114 and 115 may be defined as a third dielectric layer.

[0045] In the present disclosure, as some example embodiments of a more specific method for measuring the content of elements included in each part of the multilayer electronic component 100, in the case of a destructive method, 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) can be used to analyze each part. First, in a cross section of a sintered body or a sintered side edge portion, a thin-cut analysis sample is prepared in an area including a dielectric microstructure using a focused ion beam (FIB) device. Then, a damaged layer on the surface of the thin-cut analysis sample is removed using xenon (Xe) or argon (Ar) ion milling, and then a qualitative / quantitative analysis is performed by mapping each component to be measured in an image obtained using SEM-EDS, TEM-EDS, or STEM-EDS. In this case, the qualitative / quantitative analysis graph of each component can be expressed in terms of mass percentage (wt%), atomic percentage (at%), or molar percentage (mol%) of each element. In this case, the qualitative / quantitative analysis graph of each component can be expressed by converting the molar amount of a specific component into the molar amount of another specific component.

[0046] By another method, the chip can be crushed and the area to be measured can be selected, and in the selected area including the dielectric microstructure, the composition of the area including the dielectric microstructure can be analyzed using devices such as an inductively coupled plasma spectrometer (ICP-OES) and an inductively coupled plasma mass spectrometer (ICP-MS).

[0047] In some example embodiments of the present disclosure, the first dielectric layer 111 of the capacitance forming part Ac may not include gallium (Ga) and phosphorus (P).

[0048] Here, the fact that the first dielectric layer 111 of the capacitor forming portion Ac does not include gallium (Ga) and phosphorus (P) may mean that the dielectric slurry or the dielectric green sheet does not include gallium (Ga) and phosphorus (P) before sintering to form the first dielectric layer 111, or may mean that the first dielectric layer 111 disposed in the central region of the capacitor forming portion Ac does not include gallium (Ga) and phosphorus (P).

[0049] That is, this may mean that even if gallium (Ga) or phosphorus (P) included in the second dielectric layer of the covering portions 112 and 113 (to be described below) may diffuse into the area of ​​the first dielectric layer 111 of the capacitor forming portion Ac adjacent to the covering portions 112 and 113 due to the gallium (Ga) or phosphorus (P) being subjected to a sintering process such as high-temperature heat treatment, gallium (Ga) and phosphorus (P) may not be detected in the first dielectric layer 111 provided in the central portion of the capacitor forming portion Ac.

[0050] For example, based on the first direction and second direction cross-sections intercepted from the center of the third direction of the main body 110, when a 10μm×10μm area set in the central part of the first direction and second direction cross-sections is observed in the EDS mode of a scanning electron microscope (SEM) or a transmission electron microscope (TEM), this may indicate that gallium (Ga) and phosphorus (P) may not be detected in the corresponding area, or it may indicate that gallium (Ga) with a content of less than 0.5at% is detected in the corresponding area and phosphorus (P) with a content of less than 0.1at% is detected.

[0051] The thickness td of the dielectric layer 111 is not limited.

[0052] In order to ensure the reliability of the multilayer electronic component 100 in a high voltage environment, the thickness of the dielectric layer 111 may be less than or equal to 10.0 μm. In addition, in order to achieve miniaturization and high capacitance of the multilayer electronic component 100, the thickness of the dielectric layer 111 may be less than or equal to 3.0 μm, and in order to more easily achieve miniaturization and high capacitance, the thickness of the dielectric layer 111 may be less than or equal to 1.0 μm, preferably less than or equal to 0.6 μm, and more preferably less than or equal to 0.4 μm.

[0053] Here, the thickness td of the dielectric layer 111 may refer to a thickness td of the dielectric layer 111 disposed between the first and second internal electrodes 121 and 122 .

[0054] In addition, the thickness td of the dielectric layer 111 may refer to the first direction dimension of the dielectric layer 111. In addition, the thickness td of the dielectric layer 111 may refer to the average thickness of the dielectric layer 111, and may refer to the average dimension of the dielectric layer 111 in the first direction.

[0055] The average thickness of the dielectric layer 111 in the first direction can be measured by scanning an image of a first direction and a second direction cross section of the main body 110 using a scanning electron microscope (SEM) with a magnification of 10000 times. More specifically, the average thickness of one dielectric layer 111 in the first direction can be an average value calculated by measuring the first direction dimensions of 10 points of one dielectric layer 111 spaced apart from each other at equal intervals in the second direction in the scanned image. 10 points spaced apart from each other at equal intervals can be specified in the capacitor forming portion Ac. In addition, when the average value is measured by extending the average value measurement to 10 dielectric layers 111, the average thickness of the dielectric layer 111 in the first direction can be further generalized.

[0056] The internal electrodes 121 and 122 may be alternately stacked with the dielectric layers 111 .

[0057] The internal electrodes 121 and 122 may include first and second internal electrodes 121 and 122 which may be alternately arranged to face each other with the dielectric layer 111 interposed therebetween and may be exposed to the third and fourth surfaces 3 and 4 of the body 110 , respectively.

[0058] More specifically, the first inner electrode 121 may be spaced apart from the fourth surface 4 and may be exposed through the third surface 3, and the second inner electrode 122 may be spaced apart from the third surface 3 and may be exposed through the fourth surface 4. The first outer electrode 131 may be disposed on the third surface 3 of the body 110 and may be connected to the first inner electrode 121, and the second outer electrode 132 may be disposed on the fourth surface 4 of the body 110 and may be connected to the second inner electrode 122.

[0059] That is, the first internal electrode 121 may be connected to the first external electrode 131 without being connected to the second external electrode 132, and the second internal electrode 122 may be connected to the second external electrode 132 without being connected to the first external electrode 131. In this case, the first internal electrode 121 and the second internal electrode 122 may be electrically separated from each other by the dielectric layer 111 disposed therebetween.

[0060] In addition, the body 110 may be formed by alternately stacking ceramic green sheets on which the conductive paste for the first internal electrode 121 is printed and ceramic green sheets on which the conductive paste for the second internal electrode 122 is printed and then sintering the ceramic green sheets.

[0061] The material included in the internal electrodes 121 and 122 is not particularly limited, and any material having excellent conductivity may be used. For example, the internal electrodes 121 and 122 may include one or more selected from the group consisting of nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), gold (Au), platinum (Pt), tin (Sn), tungsten (W), titanium (Ti), and alloys thereof.

[0062] In addition, the internal electrodes 121 and 122 may be formed by printing a conductive paste for internal electrodes (including 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) on a ceramic green sheet. The method of printing the conductive paste for the internal electrodes may be a screen printing method or a gravure printing method, but the present disclosure is not limited thereto.

[0063] In addition, the thickness te of the internal electrodes 121 and 122 is not limited.

[0064] In order to ensure the reliability of the multilayer electronic component 100 in a high voltage environment, the thickness te of the internal electrodes 121 and 122 may be less than or equal to 3.0 μm. In addition, 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 less than or equal to 1.0 μm, and in order to more easily achieve ultra-miniaturization and high capacitance, the thickness of the internal electrodes 121 and 122 may be less than or equal to 0.6 μm, and may more preferably be less than or equal to 0.4 μm.

[0065] Here, the thickness te of the internal electrodes 121 and 122 may refer to the first direction size of the internal electrodes 121 and 122. In addition, the thickness te of the internal electrodes 121 and 122 may refer to the average thickness of the internal electrodes 121 and 122 and may refer to the average size of the internal electrodes 121 and 122 in the first direction.

[0066] The average size of the internal electrodes 121 and 122 in the first direction may be measured by scanning an image of a first direction and a second direction cross section of the body 110 using 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 may be an average value calculated by measuring the first direction size of one internal electrode at 10 points spaced apart from each other at equal intervals in the second direction in the scanned image. 10 points spaced apart from each other at equal intervals may be specified in the capacitor forming portion Ac. In addition, when the average value is measured by extending the average value measurement to 10 internal electrodes, the average thickness of the internal electrode in the first direction may be further generalized.

[0067] Furthermore, in some example embodiments of the present disclosure, an average thickness td of at least one of the plurality of dielectric layers 111 and an average thickness te of at least one of the plurality of internal electrodes 121 and 122 may satisfy 2×te <td。

[0068] In other words, the average thickness td of one dielectric layer 111 may be greater than twice the average thickness te of one internal electrode 121 or 122. Preferably, the average thickness td of the plurality of dielectric layers 111 may be greater than twice the average thickness te of the plurality of internal electrodes 121 and 122.

[0069] Generally, a major problem of high voltage electronic components is a reliability problem due to a decrease in breakdown voltage (BDV) in a high voltage environment.

[0070] Therefore, in order to prevent the breakdown voltage from decreasing under a high voltage environment, the average thickness td of the dielectric layer 111 can be made greater than twice the average thickness te of the internal electrodes 121 and 122, so that the thickness of the dielectric layer (as the distance between the internal electrodes) can be increased, thereby improving the breakdown voltage (BDV) characteristics.

[0071] 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 (being the distance between the internal electrodes) may be thin, which may reduce the breakdown voltage, and a short circuit may occur between the internal electrodes.

[0072] In addition, the body 110 may include cover portions 112 and 113 disposed on both surfaces (upper and lower surfaces) of the capacitance forming portion Ac in the first direction.

[0073] Specifically, the main body 110 may include a first covering portion (upper covering portion) 112 arranged on a surface (upper surface) of the capacitor forming portion Ac in the first direction and a second covering portion (lower covering portion) 113 arranged on another surface (lower surface) of the capacitor forming portion Ac in the first direction. That is, the main body 110 may include an upper covering portion 112 arranged above the capacitor forming portion Ac in the first direction and a lower covering portion 113 arranged below the capacitor forming portion Ac in the first direction.

[0074] The first cover portion 112 and the second cover portion 113 may be formed by stacking a single dielectric layer or two or more dielectric layers on the upper surface and the lower surface of the capacitance forming portion Ac in the first direction, respectively.

[0075] As described above, in the present disclosure, the dielectric layer included in the cover parts 112 and 113 may be defined as a second dielectric layer.

[0076] The first cover 112 and the second cover 113 may mainly serve to prevent damage to the internal electrodes 121 and 122 due to physical stress or chemical stress.

[0077] The first cover 112 and the second cover 113 do not include the internal electrodes 121 and 122 , and may include the same material as the first dielectric layer 111 .

[0078] That is, the first cover 112 and the second cover 113 may include a dielectric material, and may include, for example, a dielectric material based on barium titanate (BaTiO3). In addition, according to the purpose of the present disclosure, various ceramic additives, organic solvents, adhesives, dispersants, etc. may be added to particles such as barium titanate (BaTiO3) as a material included in the second dielectric layer.

[0079] In addition, the second dielectric layer included in the first cover 112 and the second cover 113 may be formed using a dielectric material such as barium titanate (BaTiO3), and thus may include a dielectric microstructure after sintering. The dielectric microstructure may include a plurality of grains, grain boundaries disposed between adjacent grains, and a triple intersection disposed at a point where three or more grain boundaries contact each other, and the number of each of the grains, grain boundaries, and triple intersections included in the dielectric microstructure may be more than one. In addition, the second dielectric layer may include a second phase that is not solid-dissolved in the grains.

[0080] In addition, the cover parts 112 and 113 may include gallium (Ga).

[0081] More specifically, the molar amount of gallium (Ga) included in the cover parts 112 and 113 may be greater than or equal to 0.3 mol and less than or equal to 6.0 mol relative to 100 mol of titanium (Ti).

[0082] Since the covering parts 112 and 113 include gallium (Ga), the sintering temperature can be lowered to reduce the number of pores, so that the compactness of the covering parts 112 and 113 can be improved, thereby improving moisture resistance reliability. In addition, even when the covering parts 112 and 113 are subjected to external impact, the generation of cracks can be suppressed, so that the mechanical properties can be improved.

[0083] Since the molar amount of gallium (Ga) included in the covering parts 112 and 113 relative to 100 moles of titanium (Ti) satisfies 0.3 moles or more and 6.0 moles or less, the sintering temperature of the covering parts 112 and 113 can be reduced to reduce the number of pores, so that the compactness of the covering parts 112 and 113 can be improved, thereby improving the moisture resistance reliability. In addition, even when the covering parts 112 and 113 are subjected to external impact, the generation of cracks can be suppressed, so that the mechanical properties can be improved.

[0084] When the molar amount of gallium (Ga) included in the covering portions 112 and 113 is less than 0.3 mol relative to 100 mol of titanium (Ti), there may be a risk that reliability may deteriorate due to degradation of grain boundary resistance due to grain growth, or there may be a risk that moisture resistance reliability may be reduced due to insufficient removal of pores.

[0085] When the molar amount of gallium (Ga) included in the covering portions 112 and 113 exceeds 6.0 moles relative to 100 moles of titanium (Ti), excessive addition of gallium (Ga) may reduce the dispersibility in the dielectric slurry state and cause agglomeration, which may cause a decrease in breakdown voltage (BDV) or cause grain growth to be excessively inhibited, resulting in reduced density, and may cause the side effect of reducing moisture resistance reliability.

[0086] In addition, the cover parts 112 and 113 may include phosphorus (P).

[0087] More specifically, the molar amount of phosphorus (P) included in the covering portions 112 and 113 relative to 100 moles of titanium (Ti) may be greater than 0 mole and less than or equal to 5.0 moles, and the upper limit may preferably be less than or equal to 3.0 moles or less than or equal to 1.0 mole, and may more preferably be less than or equal to 0.5 moles.

[0088] Since the covers 112 and 113 include phosphorus (P), the number of pores can be reduced, and thus the compactness of the covers 112 and 113 can be improved, thereby improving moisture resistance reliability. In addition, even when the covers 112 and 113 are subjected to external impact, the generation of cracks can be suppressed, thereby improving mechanical properties.

[0089] The molar amount of phosphorus (P) included in the covers 112 and 113 relative to 100 moles of titanium (Ti) may satisfy greater than 0 mole and less than or equal to 5.0 moles, thereby reducing the number of pores, thereby improving the compactness of the covers 112 and 113 and improving moisture resistance reliability.

[0090] When the molar amount of phosphorus (P) included in the capping portions 112 and 113 exceeds 5.0 mol relative to 100 mol of titanium (Ti), this may excessively inhibit grain growth and may cause a decrease in electrical characteristics such as a breakdown voltage (BDV).

[0091] In addition, as described above, the first covering portion 112 and the second covering portion 113 may include a plurality of grains having a core-shell structure, grain boundaries arranged between adjacent grains, triple intersections arranged at points where three or more grain boundaries contact each other, and a second phase, and at least one of the shell portion, grain boundaries, triple intersections, and the second phase of the core-shell structure included in the first covering portion 112 and the second covering portion 113 may include a region where the content of phosphorus (P) is less than 0.1 at %.

[0092] This may mean that phosphorus (P) is uniformly dispersed without agglomeration.

[0093] In some example embodiments of the present disclosure, the covering portions 112 and 113 may preferably include both gallium (Ga) and phosphorus (P), and in this case, the molar amount of gallium (Ga) included in the covering portions 112 and 113 relative to 100 moles of titanium (Ti) may preferably be greater than or equal to 0.3 moles and less than or equal to 6.0 moles, and the molar amount of phosphorus (P) included in the covering portions 112 and 113 relative to 100 moles of titanium (Ti) may preferably be greater than 0 moles and less than or equal to 5.0 moles, but the present disclosure is not particularly limited thereto.

[0094] In addition, a ratio (A / B) of a molar amount (A) of barium (Ba) to a molar amount (B) of titanium (Ti) included in the covering parts 112 and 113 may satisfy 0.99≤a / B≤1.05.

[0095] The ratio (A / B) of the molar amount (A) of barium (Ba) to the molar amount (B) of titanium (Ti) included in the covering parts 112 and 113 satisfies 0.99≤A / B≤1.05, which can cause uniform grain growth and improve the density of the dielectric microstructure, thereby improving reliability including moisture resistance reliability.

[0096] When the ratio (A / B) of the molar amount (A) of barium (Ba) to the molar amount (B) of titanium (Ti) included in the covering portions 112 and 113 is less than 0.99 (A / B<0.99), there is a risk that electrical characteristics such as breakdown voltage (BDV) may be deteriorated due to uneven grain growth, and when the ratio (A / B) of the molar amount (A) of barium (Ba) to the molar amount (B) of titanium (Ti) included in the covering portions 112 and 113 is greater than 1.05 (1.05

[0097] In addition, since the cover portions 112 and 113 include at least one of gallium (Ga) and phosphorus (P), the composition of the second dielectric layer included in the cover portions 112 and 113 may be different from the composition of the first dielectric layer included in the capacitance forming portion Ac.

[0098] In other words, a molar amount of gallium (Ga) included in the second dielectric layer relative to 100 moles of titanium (Ti) may be greater than a molar amount of gallium (Ga) included in the first dielectric layer relative to 100 moles of titanium (Ti).

[0099] ​In addition, a molar amount of phosphorus (P) included in the second dielectric layer relative to 100 moles of titanium (Ti) may be greater than a molar amount of phosphorus (P) included in the first dielectric layer relative to 100 moles of titanium (Ti).

[0100] In some example embodiments of the present disclosure, the grain boundaries of the capping portions 112 and 113 may include a region where the atomic percentage (at%) of gallium (Ga) is greater than or equal to 2.0 at %, and the upper limit thereof is not particularly limited but may be, for example, less than or equal to 4.0 at %.

[0101] Since the grain boundaries of the covering parts 112 and 113 include a region where the atomic percentage (at%) of gallium (Ga) is greater than or equal to 2.0 at%, the sintering temperature can be lowered to reduce the number of pores, so that the compactness of the covering parts 112 and 113 can be improved, thereby improving moisture resistance reliability. In addition, even when the covering parts 112 and 113 are subjected to external impact, the generation of cracks can be suppressed, so that the mechanical properties can be improved.

[0102] In addition, an average atomic percentage (at%) of gallium (Ga) included in the grain boundaries of the cover parts 112 and 113 may be greater than or equal to 0.5 at % and less than or equal to 2.0 at %.

[0103] Since the average atomic percentage (at%) of gallium (Ga) included in the grain boundaries of the covering parts 112 and 113 satisfies 0.5 at% or more and 2.0 at% or less, the sintering temperature can be reduced to reduce the number of pores, so that the compactness of the covering parts 112 and 113 can be improved, thereby improving the moisture resistance reliability. In addition, even when the covering parts 112 and 113 are subjected to external impact, the generation of cracks can be suppressed, so that the mechanical properties can be improved.

[0104] Here, the method of measuring the atomic percentage (at%) of gallium (Ga) included in the grain boundaries of the cover portions 112 and 113 is not particularly limited, but the EDS analysis method as described above may be used. The EDS analysis position may be confirmed by measuring a point of the grain boundary, or a line profile (a method of analyzing the composition of a line drawn in a direction perpendicular to the actual line shape of the grain boundary provided between adjacent grains) may be used to obtain the EDS analysis position, and the atomic percentage (at%) of gallium (Ga) may be confirmed in the measured line profile.

[0105] In addition, the thickness tc of the covering portions 112 and 113 is not limited.

[0106] However, to more easily achieve miniaturization and high capacitance of multilayer electronic components, in ultra-small products, the thickness tc of the covers 112 and 113 may be 100 μm or less, preferably 30 μm or less, and more preferably 20 μm or less.

[0107] Here, the thickness tc of the covering parts 112 and 113 may refer to the first direction dimension of the covering parts 112 and 113 in the first direction. In addition, the thickness tc of the covering parts 112 and 113 may refer to the average thickness of the covering parts 112 and 113, and may refer to the average dimension of the covering parts 112 and 113 in the first direction.

[0108] The average size of the covering portions 112 and 113 in the first direction may be measured by scanning an image of a first direction and a second direction cross section of the body 110 using a scanning electron microscope (SEM) at a magnification of 10,000 times. More specifically, the average size of the covering portions 112 and 113 in the first direction may refer to an average value calculated by measuring the first direction size at 10 points equally spaced from each other in the second direction in an image obtained by scanning one covering portion.

[0109] In addition, the average size of the covering portion in the first direction measured by the above method may have substantially the same size as the average size of the covering portion in the first and third direction cross sections of the body 110 in the first direction.

[0110] Furthermore, the multilayer electronic component 100 may include side edge portions 114 and 115 disposed on both third-direction surfaces of the capacitance forming portion Ac.

[0111] More specifically, the side edge portions 114 and 115 may include a first side edge portion 114 disposed on one surface of the capacitor forming portion Ac in the third direction and a second side edge portion 115 disposed on another surface of the capacitor forming portion Ac in the third direction to respectively form a fifth surface 5 and a sixth surface 6 of the body 110.

[0112] like Figure 4 As shown, the side edge portions 114 and 115 may refer to regions between both ends of the first and second internal electrodes 121 and 122 in the third direction and the outer surface of the body 110 based on the first and third direction sections of the body 110 .

[0113] More specifically, in order to suppress the step portions caused by the internal electrodes 121 and 122, the side edge portions 114 and 115 may be formed in the following manner: a conductive paste for forming the internal electrodes 121 and 122 is coated on areas of the ceramic green sheets other than areas where the side edge portions 114 and 115 are to be formed, the ceramic green sheets are stacked to form a stack of ceramic green sheets including a capacitor forming portion Ac, and then the stack is cut so that the internal electrodes 121 and 122 are exposed to two third directional surfaces of the capacitor forming portion Ac, and then a single third dielectric layer or two or more third dielectric layers are stacked along the third direction on the two third directional surfaces of the capacitor forming portion Ac.

[0114] As described above, in the present disclosure, the dielectric layer included in the side margin parts 114 and 115 may be defined as a third dielectric layer.

[0115] The side margin parts 114 and 115 may mainly serve to prevent damage to the internal electrodes 121 and 122 due to physical stress or chemical stress.

[0116] The first and second side margin portions 114 and 115 do not include the internal electrodes 121 and 122 , and may include the same material as the dielectric layer 111 .

[0117] That is, the first side edge portion 114 and the second side edge portion 115 may include a dielectric material, and may include, for example, a dielectric material based on barium titanate (BaTiO3). In addition, according to the purpose of the present disclosure, various ceramic additives, organic solvents, adhesives, dispersants, etc. may be added to particles such as barium titanate (BaTiO3) as a material included in the third dielectric layer.

[0118] In addition, the third dielectric layer included in the side edge portions 114 and 115 may be formed using a dielectric material such as barium titanate (BaTiO3), and may include a dielectric microstructure after sintering. The dielectric microstructure may include a plurality of crystal grains, grain boundaries disposed between adjacent crystal grains, and triple intersections disposed at points where three or more crystal boundaries contact each other, and the number of each of the crystal grains, grain boundaries, and triple intersections included in the dielectric microstructure may be more than one.

[0119] However, the composition of the third dielectric layer may be different from that of the second dielectric layer, for example, the third dielectric layer included in the side margin parts 114 and 115 may not include gallium (Ga) and phosphorus (P).

[0120] Therefore, the composition of the second dielectric layer included in the cover parts 112 and 113 may be different from the composition of the third dielectric layer included in the side margin parts 114 and 115 .

[0121] In other words, a molar amount of gallium (Ga) included in the second dielectric layer relative to 100 moles of titanium (Ti) may be greater than a molar amount of gallium (Ga) included in the third dielectric layer relative to 100 moles of titanium (Ti).

[0122] In addition, a molar amount of phosphorus (P) included in the second dielectric layer relative to 100 moles of titanium (Ti) may be greater than a molar amount of phosphorus (P) included in the third dielectric layer relative to 100 moles of titanium (Ti).

[0123] Here, the fact that the third dielectric layer of the side edge portions 114 and 115 does not include gallium (Ga) and phosphorus (P) may mean that the dielectric slurry or the dielectric green sheet does not include gallium (Ga) and phosphorus (P) before sintering to form the third dielectric layer, or may mean that the third dielectric layer disposed in the central region of the side edge portions 114 and 115 does not include gallium (Ga) and phosphorus (P).

[0124] That is, this may mean that even if gallium (Ga) or phosphorus (P) included in the second dielectric layer of the above-mentioned covering portions 112 and 113 may diffuse into the area of ​​the third dielectric layer of the side edge portions 114 and 115 adjacent to the covering portions 112 and 113 due to the gallium (Ga) or phosphorus (P) being subjected to a sintering process such as high-temperature heat treatment, gallium (Ga) and phosphorus (P) may not be detected in the third dielectric layer provided in the central area of ​​the side edge portions 114 and 115.

[0125] For example, based on the first and third direction cross sections taken from the center of the second direction of the multilayer electronic component 100, when a 5μm×5μm area in the central portion of the first and third direction cross sections of the side edges 114 and 115 is observed using an energy dispersive X-ray spectroscopy (EDS) mode of a scanning electron microscope (SEM) or a transmission electron microscope (TEM), this may indicate that gallium (Ga) and phosphorus (P) are not detected in the corresponding area, or may indicate that gallium (Ga) with a content of less than 0.5at% is detected in the corresponding area and phosphorus (P) with a content of less than 0.1at% is detected.

[0126] In addition, the width wm of the first side margin portion 114 and the second side margin portion 115 is not limited.

[0127] However, in order to more easily achieve miniaturization and high capacitance of the multilayer electronic component 100 , in ultra-small products, the width wm of the side edge portions 114 and 115 may be 100 μm or less, preferably 30 μm or less, and more preferably 20 μm or less.

[0128] Here, the width wm of the side margin portions 114 and 115 may refer to the third direction dimension of the side margin portions 114 and 115. In addition, the width wm of the side margin portions 114 and 115 may refer to the average width of the side margin portions 114 and 115, and may refer to the average dimension of the side margin portions 114 and 115 in the third direction.

[0129] The average size of the side edge portions 114 and 115 in the third direction may be measured by scanning an image of the first and third direction cross-sections of the body 110 using a scanning electron microscope (SEM) at a magnification of 10,000 times. More specifically, the average size of the side edge portions 114 and 115 in the third direction may refer to an average value calculated by measuring the third direction size at 10 points equally spaced from each other in the first direction in an image obtained by scanning one side edge portion.

[0130] In some example embodiments of the present disclosure, a structure in which the multilayer electronic component 100 has two external electrodes 131 and 132 is described, but the number or shape of the external electrodes 131 and 132 may be changed according to the shapes of the internal electrodes 121 and 122 or other purposes.

[0131] The external electrodes 131 and 132 may be disposed on the body 110 , and may be connected to the internal electrodes 121 and 122 .

[0132] More specifically, the external electrodes 131 and 132 may be disposed on the third surface 3 and the fourth surface 4 of the body 110, respectively, and may include a first external electrode 131 and a second external electrode 132 respectively connected to the first internal electrode 121 and the second internal electrode 122. That is, the first external electrode 131 may be disposed on the third surface 3 of the body and may be connected to the first internal electrode 121, and the second external electrode 132 may be disposed on the fourth surface 4 of the body and may be connected to the second internal electrode 122.

[0133] In addition, the external electrodes 131 and 132 may be provided to extend to a portion of the first surface 1 and a portion of the second surface 2 of the body 110, and may also be provided to extend to a portion of the fifth surface 5 and a portion of the sixth surface 6 of the body 110. That is, the first external electrode 131 may be provided on a portion of the first surface 1, a portion of the second surface 2, a portion of the fifth surface 5, and a portion of the sixth surface 6 of the body 110 and may be provided on the third surface 3 of the body 110, and the second external electrode 132 may be provided on a portion of the first surface 1, a portion of the second surface 2, a portion of the fifth surface 5, and a portion of the sixth surface 6 of the body 110 and may be provided on the fourth surface 4 of the body 110.

[0134] In addition, the external electrodes 131 and 132 may be formed using any material as long as the material has conductivity such as metal, and a specific material may be determined in consideration of electrical characteristics, structural stability, etc. In addition, the external electrodes 131 and 132 may also have a structure of at least one layer.

[0135] For example, the external electrodes 131 and 132 may include an electrode layer disposed on the body 110 and a plating layer disposed on the electrode layer.

[0136] For a more specific example of the electrode layer, the electrode layer may include first electrode layers 131a and 132a which are sintered electrodes including a first conductive metal and glass, or may include second electrode layers 131b and 132b which are resin-based electrodes including a second conductive metal and resin.

[0137] Here, the conductive metal included in the first electrode layers 131a and 132a may be referred to as a first conductive metal, and the conductive metal included in the second electrode layers 131b and 132b may be referred to as a second conductive metal. In this case, the first conductive metal and the second conductive metal may be the same as or different from each other, and when the first conductive metal and the second conductive metal include a plurality of metal materials, the first conductive metal and the second conductive metal may include at least one of the same metal materials, but the present disclosure is not particularly limited thereto.

[0138] In addition, the electrode layers 131 a , 132 a , 131 b , and 132 b may be formed by sequentially forming a sintered electrode and a resin-based electrode on the body 110 .

[0139] In addition, the electrode layers 131a, 132a, 131b, and 132b may be formed by transferring a sheet including a conductive metal onto a body, or may be formed by transferring a sheet including a conductive metal onto a sintered electrode.

[0140] A material having excellent conductivity may be used as the conductive metal included in the electrode layers 131a, 132a, 131b and 132b, for example, the conductive metal may include one or more selected from the group consisting of nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), gold (Au), platinum (Pt), tin (Sn), tungsten (W), titanium (Ti) and alloys thereof, but the present disclosure is not particularly limited thereto.

[0141] In some example embodiments of the present disclosure, the electrode layers 131a, 132a, 131b, and 132b may have a double-layer structure including first electrode layers 131a and 132a and second electrode layers 131b and 132b, and thus, the external electrodes 131 and 132 may include first electrode layers 131a and 132a and second electrode layers 131b and 132b, the first electrode layers 131a and 132a including a first conductive metal and glass, and the second electrode layers 131b and 132b are disposed on the first electrode layers 131a and 132a and including a second conductive metal and resin.

[0142] The first electrode layers 131 a and 132 a may serve to improve adhesion to the body 110 by including glass, and the second electrode layers 131 b and 132 b may serve to improve bending strength by including resin.

[0143] The first conductive metal used in the first electrode layers 131a and 132a is not particularly limited as long as the first conductive metal has a material that can be electrically connected to the internal electrodes 121 and 122 to form a capacitor, and the first conductive metal may include, for example, 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.

[0144] The first electrode layers 131 a and 132 a may be formed by coating a conductive paste prepared by adding glass frit to first conductive metal particles and then sintering the conductive paste.

[0145] The second conductive metal included in the second electrode layers 131 b and 132 b may serve to electrically connect to the first electrode layers 131 a and 132 a .

[0146] The conductive metal included in the second electrode layers 131 b and 132 b is not particularly limited as long as the conductive metal has a material that can be electrically connected to the first electrode layers 131 a and 132 a, and the conductive metal may include one or more selected from the group consisting of nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), gold (Au), platinum (Pt), tin (Sn), tungsten (W), titanium (Ti) and alloys thereof.

[0147] The second conductive metal included in the second electrode layers 131b and 132b may include at least one of spherical particles and flaky particles. That is, the second conductive metal may consist of only flaky particles or only spherical particles, and may be a mixture of flaky particles and spherical particles. Here, the spherical particles may include an incomplete spherical shape, such as a shape in which the length ratio of the major axis to the minor axis (major axis length / minor axis length) is less than or equal to 1.45. Flaky particles may refer to particles having a flat and elongated shape, and the present disclosure is not particularly limited, for example, it may be a particle having a length ratio of the major axis to the minor axis (major axis length / minor axis length) greater than or equal to 1.95. The lengths of the major and minor axes of the spherical particles and the flaky particles may be measured from an image obtained by scanning a first direction and a second direction section cut from the central portion of the multilayer electronic component in the third direction using a scanning electron microscope (SEM).

[0148] The resin included in the second electrode layers 131b and 132b may ensure bonding and function as an impact absorber. The resin included in the second electrode layers 131b and 132b may have bonding and impact absorbency, and the resin is not particularly limited as long as the resin can be mixed with the second conductive metal particles to make a paste, and may include, for example, an epoxy resin.

[0149] In addition, the second electrode layers 131b and 132b may include a plurality of second conductive metal particles, an intermetallic compound, and a resin. The intermetallic compound may be included to further improve electrical connectivity with the first electrode layers 131a and 132a. The intermetallic compound may be used to improve electrical connectivity by connecting a plurality of metal particles, and may be used to surround a plurality of metal particles and connect the metal particles to each other.

[0150] In this case, the intermetallic compound may include a metal having a melting point lower than the solidification temperature of the resin. That is, because the intermetallic compound includes a metal having a melting point lower than the solidification temperature of the resin, the metal having a melting point lower than the solidification temperature of the resin melts during the drying and solidification process and forms the intermetallic compound with a portion of the metal particles to surround the metal particles. In this case, the intermetallic compound may preferably include a low melting point metal (melting point equal to or less than 300° C.).

[0151] For example, the intermetallic compound may include Sn having a melting point of 213° C. to 220° C. Sn melts during the drying and solidification process, and the molten Sn wets high melting point metal particles (such as Ag, Ni, or Cu) by capillary action and reacts with some of the Ag, Ni, or Cu metal particles to form an intermetallic compound (such as Ag3Sn, Ni3Sn4, Cu6Sn5, and Cu3Sn). Ag, Ni, or Cu that does not participate in the reaction remains in the form of metal particles.

[0152] Therefore, the plurality of second conductive metal particles may include one or more of Ag, Ni, and Cu, and the intermetallic compound may include one or more of Ag3Sn, Ni3Sn4, Cu6Sn5, and Cu3Sn.

[0153] The plating layers 131c and 132c may be used to improve mounting characteristics.

[0154] The type of the plating layers 131c and 132c is not particularly limited, and may include one or more of nickel (Ni), tin (Sn), silver (Ag), palladium (Pd), and alloys thereof. In addition, the plating layers 131c and 132c may have a single layer structure or a multilayer structure.

[0155] For a more specific example of the plating layers 131c and 132c, the plating layers 131c and 132c may be a Ni plating layer or a Sn plating layer formed on the electrode layer, or may be a Ni plating layer and a Sn plating layer sequentially formed on the electrode layer, or may be a Sn plating layer, a Ni plating layer, and a Sn plating layer sequentially formed on the electrode layer. In addition, the plating layers 131c and 132c may include a plurality of Ni plating layers and / or a plurality of Sn plating layers.

[0156] The size of the multilayer electronic component 100 does not need to be particularly limited.

[0157] However, in order to achieve both miniaturization and high capacitance, the thickness of the dielectric layer and the internal electrode must be thinned to increase the number of stacked layers, so the effect according to the present disclosure may be more obvious in a multilayer electronic component 100 having a size of 3216 (length×width: 3.2 mm×1.6 mm) or smaller.

[0158] Hereinafter, the present disclosure will be described in more detail through examples, but this is intended to help specific understanding of the present disclosure, and the scope of the present disclosure is not limited to the example embodiments.

[0159] <Example Embodiment>

[0160] In Comparative Example 1, a multilayer electronic component including a cover portion and a side edge portion was manufactured, and a chip was prepared by manufacturing the multilayer electronic component without adding gallium (Ga) and phosphorus (P) to the cover portion and the side edge portion.

[0161] In Inventive Example 1, a chip was prepared by manufacturing a multilayer electronic component in the following manner: gallium (Ga) was added to the cover in an amount of 0.3 mol or more and 6.0 mol or less relative to 100 mol of titanium (Ti), and phosphorus (P) was added to the cover in an amount of 0 mol or more and 5.0 mol or less relative to 100 mol of titanium (Ti). Except for this, the chip was manufactured in the same manner as in Comparative Example 1.

[0162] Figure 5A are images of cross sections in the first and third directions of the upper cover portion of Comparative Example 1 captured in a High-Angle Annular Dark-Field (HAADF) mode of a transmission electron microscope (TEM), Figure 5B is through Figure 5A An image obtained by performing EDS analysis in a region to map the aluminum (Al) element, and Figure 5C is through Figure 5A An image obtained by performing EDS analysis in a region of φ1 to map the silicon (Si) element.

[0163] Fig. 6A are images of cross sections in the first and third directions of the upper cover portion of Inventive Example 1 captured in the HAADF mode of a transmission electron microscope (TEM), Figure 6B is through Fig. 6A An image obtained by performing EDS analysis in an area to map the aluminum (Al) element, Figure 6C is through Fig. 6A An image obtained by performing EDS analysis in a region to map the silicon (Si) element, and Fig.6D is through Fig. 6AAn image obtained by performing EDS analysis in a region of 20° to map the gallium (Ga) element.

[0164] Figure 7 Corresponding to Fig. 6A different regions, and are images obtained by capturing images of first and second direction cross sections of the upper cover portion of Inventive Example 1 using a transmission electron microscope (TEM) and then performing EDS analysis to map the phosphorus (P) element.

[0165] In Comparative Example 1 and Inventive Example 1, when the covering portion includes gallium (Ga), it can be seen that gallium (Ga) is arranged in the shell portion of the core-shell grains, the interior of the grains, the grain boundaries, and the triple intersections, and since gallium (Ga) is detected together in the areas where silicon (Si) and aluminum (Al) are detected, it can be seen that gallium (Ga) is arranged in the second phase including silicon (Si) and aluminum (Al).

[0166] In addition, when the covering parts 112 and 113 include phosphorus (P), it can be seen that the phosphorus (P) may be disposed in the shell portion of the core-shell grains, the interior of the grains, the grain boundaries, and the triple intersections. Figure 7 It can be seen that phosphorus (P) is observed in a region of a fixed area, which means that the second phase disposed in at least one of the grain boundaries or the triple intersections includes phosphorus (P), which means that phosphorus (P) can be disposed in at least one of the grain boundaries and the triple intersections.

[0167] Next, in Comparative Examples 2 and 3, 28 chips were each manufactured under the same conditions as in Comparative Example 1, and in Inventive Examples 2 and 3, 28 chips were each manufactured under the same conditions as in Inventive Example 1.

[0168] For Comparative Example 2 and Inventive Example 2, moisture resistance reliability evaluation was performed, and for Comparative Example 3 and Inventive Example 3, a highly accelerated life test (HALT, a reliability evaluation under severe conditions) was performed.

[0169] Fig. 8A is a moisture resistance reliability evaluation diagram of Comparative Example 2, Figure 8B This is a moisture resistance reliability evaluation diagram of Inventive Example 2.

[0170] In the moisture resistance reliability evaluation, a chip in which a short circuit occurred after applying an evaluation voltage of 1.5 Vr (ie, 1.5 times the rated voltage) under the temperature conditions of 85° C. and the relative humidity conditions of 85% for 26 hours was evaluated as a defect.

[0171] Fig.9A This is a reliability evaluation diagram of Comparative Example 3 under harsh conditions. Fig. 9B This is a reliability evaluation diagram under severe conditions of Invention Example 3.

[0172] In the HALT evaluation, after applying an evaluation voltage of 1.5 Vr for 30 hours under a temperature condition of 125° C., a chip in which a short circuit occurred was evaluated as a defect, and the mean time to failure (MTTF) was obtained by averaging the time in which the short circuit occurred.

[0173] In Comparative Example 2, short circuits occurred in all 28 samples, whereas in Inventive Example 2, short circuits occurred in 8 of the 28 samples.

[0174] Next, in the case of Comparative Example 3, the mean time to failure (MTTF) was 1.6 hours, whereas in Inventive Example 3, the mean time to failure (MTTF) was 16.6 hours, which increased the lifespan by about 10.4 times compared to Comparative Example 3.

[0175] Thus, when the molar amount of gallium (Ga) included in the covering portion relative to 100 moles of titanium (Ti) is greater than or equal to 0.3 moles and less than or equal to 6.0 moles and the molar amount of phosphorus (P) included in the covering portion relative to 100 moles of titanium (Ti) is greater than 0 moles and less than or equal to 5.0 moles, it can be seen that moisture resistance reliability and mean time to failure (MTTF) are improved.

[0176] Next, the contents of gallium (Ga) and phosphorus (P) included in the covering portion relative to 100 mol of titanium (Ti) were changed and listed in the following Table 1, and the slurry dispersibility, grain size, porosity, moisture resistance reliability and mean time to failure (MTTF) during HALT evaluation according to each test example were measured and listed in the following Table 2.

[0177] In Table 1, Ga corresponds to the molar amount of gallium included in the cover relative to 100 moles of titanium (Ti), and P corresponds to the molar amount of phosphorus included in the cover relative to 100 moles of titanium (Ti). When agglomerates are generated in the dielectric slurry state, the slurry dispersion is represented as "X", and when agglomerates are not generated in the dielectric slurry state, the slurry dispersion is represented as "O".

[0178] In Table 2, the grain size describes the average size of the grains in a 10μm×10μm region of the first and third direction cross-section of the covering portion. The porosity (%) is obtained by calculating the area ratio of the area of ​​the holes in the region to the total area of ​​the region in the 15μm×15μm region of the first and third direction cross-section of the covering portion by a program, and then expressing the calculated area ratio as a percentage (%). Moisture resistance reliability is recorded as follows: 28 chips are manufactured for each test example, and then an evaluation voltage of 1.5Vr is applied for 26 hours under a temperature condition of 85°C and a relative humidity condition of 85%, and the number of chips that short-circuit is counted. MTTF is obtained and recorded as follows: 28 chips are manufactured for each test example, and then a HALT evaluation is performed in which an evaluation voltage of 1.5Vr is applied for 30 hours under a temperature condition of 125°C, and the time when the chips short-circuit is averaged.

[0179] [Table 1]

[0180] Test No. Ga(mol) P(mol) Slurry dispersion Test Example 1 0 0 ○ Test Example 2 0.3 0 ○ Test Example 3 0.3 0.14 ○ Test Example 4 0.6 0 ○ Test Example 5 0.6 0.14 ○ Test Example 6 0.9 0 ○ Test Example 7 0.9 0.14 ○ Test Example 8 3.0 0 ○ Test Example 9 3.0 0.14 ○ Test Example 10 3.0 0.28 ○ Test Example 11 6.0 0 ○ Test Example 12 6.0 0.14 ○ Test Example 13 6.0 0.28 ○ Test Case 14 7.0 0.14 X Test Case 15 9.0 0.14 X

[0181] [Table 2]

[0182]

[0183] When the content of gallium (Ga) included in the cover satisfies 0.3 mol or more and 6.0 mol or less relative to 100 mol of titanium (Ti), it can be seen that agglomeration of the dielectric slurry does not occur, and moisture resistance reliability and mean time to failure (MTTF) are improved.

[0184] In addition, when the content of gallium (Ga) included in the covering portion is greater than or equal to 0.3 mol and less than or equal to 6.0 mol relative to 100 mol of titanium (Ti) and the content of phosphorus (P) included in the covering portion is greater than 0 mol and less than or equal to 5.0 mol relative to 100 mol of titanium (Ti), it can be seen that this can further improve the porosity (%) and moisture resistance reliability as a whole compared to the case where phosphorus (P) is not included.

[0185] Thus, the molar amount of gallium (Ga) included in the covering portion relative to 100 moles of titanium (Ti) is greater than or equal to 0.3 moles and less than or equal to 6.0 moles and the molar amount of phosphorus (P) included in the covering portion relative to 100 moles of titanium (Ti) is greater than 0 moles and less than or equal to 5.0 moles. It can be seen that moisture resistance reliability and mean time to failure (MTTF) can be improved.

[0186] Next, while changing the ratio (A / B) of the molar amount (A) of barium (Ba) to the molar amount (B) of titanium (Ti) included in the cover, the compactness of the dielectric microstructure was evaluated and the breakdown voltage (BDV) was measured and listed in Table 3 below.

[0187] In the test example in Table 3, in addition to changing the A / B ratio, a chip was manufactured in which the molar amount of gallium (Ga) included in the covering portion relative to 100 moles of titanium (Ti) was greater than or equal to 0.3 moles and less than or equal to 6.0 moles and the molar amount of phosphorus (P) included in the covering portion relative to 100 moles of titanium (Ti) was greater than 0 moles and less than or equal to 5.0 moles.

[0188] A / B in Table 3 refers to a ratio of the number of moles (A) of barium (Ba) to the number of moles (B) of titanium (Ti) included in the covering portion.

[0189] In the first and second direction cross sections of the cover including the chip, after observing the porosity (%) of the cover using a scanning electron microscope (SEM) and capturing its image, the density is obtained using a porosity calculation program. When the porosity (%) is less than or equal to 0.30%, this is evaluated as good and recorded as "O", and when the porosity (%) is greater than 0.30%, this is evaluated as a defect and recorded as "X".

[0190] BDV was obtained by measuring the voltage (V) at which a short circuit occurred when the voltage was increased by 1 V at intervals of 0.17 seconds using a Keithley device with a current of 20 mA.

[0191] [Table 3]

[0192]

[0193]

[0194] In Test Examples 16 to 22, the ratio (A / B) of the molar amount (A) of barium (Ba) to the molar amount (B) of titanium (Ti) included in the covering portion satisfies greater than or equal to 0.99 and less than or equal to 1.05, thereby improving compactness and having excellent breakdown voltage (BDV).

[0195] Although the exemplary embodiments of the present disclosure have been described in detail above, the present disclosure is not limited to the above embodiments and the accompanying drawings, and is defined by the appended claims. Therefore, those of ordinary skill in the art may make various substitutions, modifications or changes without departing from the scope of the present disclosure defined by the appended claims, and these substitutions, modifications or changes should be interpreted as being included within the scope of the present disclosure.

[0196] In addition, the expression "exemplary embodiment" used in the present disclosure does not mean the same embodiment, and is provided to emphasize and explain different unique characteristics. However, the embodiment presented above does not exclude the combination of features with another embodiment. For example, although an item described in a particular embodiment is not described in another embodiment, unless there is a description contrary to or contradictory to the item in another embodiment, the item can be understood as a description related to another embodiment.

[0197] In the present disclosure, the terms are used only to describe specific embodiments and are not intended to limit the present disclosure. Unless the context clearly indicates otherwise, a singular form may also include a plural form.

Claims

1. A multilayer electronic component comprising: a main body including a capacitance forming part and a covering part, wherein the capacitance forming part includes a dielectric layer and inner electrodes arranged alternately with the dielectric layer in a first direction, and the covering part is arranged on both surfaces of the capacitance forming part in the first direction; and an outer electrode, disposed on the body, wherein the covering portion comprises titanium, gallium and phosphorus, and The covering portion includes 0.3 mol or more and 6.0 mol or less of gallium with respect to 100 mol of titanium.

2. The multilayer electronic component of claim 1, wherein: The coating portion includes phosphorus in an amount greater than 0 mol and equal to or less than 5.0 mol relative to 100 mol of titanium.

3. The multilayer electronic component of claim 1, wherein: The dielectric layer included in the capacitance forming portion is defined as a first dielectric layer, and the covering portion includes a second dielectric layer, and The composition of the first dielectric layer is different from the composition of the second dielectric layer.

4. The multilayer electronic component of claim 3, wherein: A molar amount of gallium included in the second dielectric layer relative to 100 moles of titanium is greater than a molar amount of gallium included in the first dielectric layer relative to 100 moles of titanium.

5. The multilayer electronic component of claim 3, wherein: A molar amount of phosphorus included in the second dielectric layer relative to 100 moles of titanium is greater than a molar amount of phosphorus included in the first dielectric layer relative to 100 moles of titanium.

6. The multilayer electronic component of claim 1, wherein: The covering portion includes a plurality of crystal grains having a core-shell structure, a crystal boundary disposed between adjacent crystal grains, a triple intersection disposed at a point where three or more crystal boundaries contact each other, and a second phase, and At least one of the shell portion of the core-shell structure, the grain boundary, the triple intersection, and the second phase includes a region in which the content of phosphorus is less than 0.1 at %.

7. The multilayer electronic component of claim 1, wherein: The covering portion further comprises barium, and A ratio A / B satisfies 0.99≦A / B≦1.05, wherein a molar amount of barium included in the covering portion is defined as A and a molar amount of titanium included in the covering portion is defined as B.

8. The multilayer electronic component of claim 1, wherein: The body includes a first surface and a second surface opposite to each other in the first direction, a third surface and a fourth surface connected to the first surface and the second surface and opposite to each other in the second direction, and a fifth surface and a sixth surface connected to the first surface, the second surface, the third surface and the fourth surface and opposite to each other in the third direction, The multilayer electronic component further includes side edge portions provided on two surfaces of the capacitance forming portion that are opposite to each other in the third direction to form the fifth surface and the sixth surface, The covering portion includes a second dielectric layer, The side edge portion includes a third dielectric layer, The composition of the second dielectric layer is different from the composition of the third dielectric layer.

9. The multilayer electronic component of claim 8, wherein: A molar amount of gallium included in the second dielectric layer relative to 100 moles of titanium is greater than a molar amount of gallium included in the third dielectric layer relative to 100 moles of titanium.

10. The multilayer electronic component of claim 8, wherein: A molar amount of phosphorus included in the second dielectric layer relative to 100 moles of titanium is greater than a molar amount of phosphorus included in the third dielectric layer relative to 100 moles of titanium.

11. A multilayer electronic component comprising: a main body including a capacitance forming part and a covering part, the capacitance forming part including a dielectric layer and inner electrodes arranged alternately with the dielectric layer in a first direction, the covering part being arranged on an upper surface and a lower surface of the capacitance forming part in the first direction; and an outer electrode, disposed on the body, wherein the covering portion comprises titanium, gallium and phosphorus, and The coating portion includes phosphorus in an amount greater than 0 mol and equal to or less than 5.0 mol relative to 100 mol of titanium.

12. The multilayer electronic component of claim 11, wherein: The dielectric layer included in the capacitance forming portion is defined as a first dielectric layer, and the covering portion includes a second dielectric layer, and The composition of the first dielectric layer is different from the composition of the second dielectric layer.

13. The multilayer electronic component of claim 12, wherein: The molar amount of gallium included in the second dielectric layer relative to 100 moles of titanium is greater than the molar amount of gallium included in the first dielectric layer relative to 100 moles of titanium.

14. The multilayer electronic component of claim 12, wherein: A molar amount of phosphorus included in the second dielectric layer relative to 100 moles of titanium is greater than a molar amount of phosphorus included in the first dielectric layer relative to 100 moles of titanium.

15. The multilayer electronic component of claim 11, wherein: The covering portion includes a plurality of crystal grains having a core-shell structure, a crystal boundary disposed between adjacent crystal grains, a triple intersection disposed at a point where three or more crystal boundaries contact each other, and a second phase, and At least one of the shell portion of the core-shell structure, the grain boundary, the triple intersection, and the second phase includes a region in which the content of phosphorus is less than 0.1 at %.

16. The multilayer electronic component of claim 11, wherein: The covering portion further comprises barium, and A ratio A / B satisfies 0.99≦A / B≦1.05, wherein a molar amount of barium included in the covering portion is defined as A and a molar amount of titanium included in the covering portion is defined as B.

17. The multilayer electronic component of claim 11, wherein: The body includes a first surface and a second surface opposite to each other in the first direction, a third surface and a fourth surface connected to the first surface and the second surface and opposite to each other in the second direction, and a fifth surface and a sixth surface connected to the first surface, the second surface, the third surface and the fourth surface and opposite to each other in the third direction, The multilayer electronic component further includes side edge portions provided on two surfaces of the capacitance forming portion that are opposite to each other in the third direction to form the fifth surface and the sixth surface, The cover portion includes a second dielectric layer, and the side edge portion includes a third dielectric layer, The composition of the second dielectric layer is different from the composition of the third dielectric layer.

18. The multilayer electronic component of claim 17, wherein: A molar amount of gallium included in the second dielectric layer relative to 100 moles of titanium is greater than a molar amount of gallium included in the third dielectric layer relative to 100 moles of titanium.

19. The multilayer electronic component of claim 17, wherein: A molar amount of phosphorus included in the second dielectric layer relative to 100 moles of titanium is greater than a molar amount of phosphorus included in the third dielectric layer relative to 100 moles of titanium.

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