KR20240094947A - Ceramic electronic component and manufacturing method thereof - Google Patents

Abstract

A ceramic electronic component according to an embodiment of the present invention includes a body including a dielectric layer and internal electrodes alternately disposed with the dielectric layer; and an external electrode disposed on the body; The dielectric layer includes a first region extending from the interface with the internal electrode to 50 nm in the inner direction of the dielectric layer and a second region excluding the first region, and oxygen in the first region is The average In content compared to all elements except oxygen may be 0.5 at% or more and 2.0 at% or less, and the average Sn content compared to all elements excluding oxygen may be 0.5 at% or more and 1.75 at% or less.

Description

Ceramic electronic components and manufacturing method thereof {CERAMIC ELECTRONIC COMPONENT AND MANUFACTURING METHOD THEREOF}

The present invention relates to ceramic electronic components and methods for manufacturing the same.

Multi-Layered Ceramic Capacitor (MLCC), one of the ceramic electronic components, is used in video devices such as liquid crystal displays (LCDs) and plasma display panels (PDPs), computers, and smartphones. It is a chip-type condenser that is mounted on the printed circuit board of various electronic products such as mobile phones and phones to charge or discharge electricity.

These multilayer ceramic capacitors can be used as components in various electronic devices due to their small size, high capacity, and easy mounting. As various electronic devices such as computers and mobile devices become smaller and have higher output, the demand for miniaturization and higher capacity for multilayer ceramic capacitors is increasing.

Recently, the technology of electric vehicles (EV, HEV, PHEV, etc.) is gradually increasing and the penetration rate is increasing, and the demand for semiconductors and electronic passive devices is also rapidly increasing. Unlike electronic passive devices for IT, devices for electric vehicles must operate without error in high temperature/high pressure/high humidity environments, and the development of materials that can achieve ultra-high reliability at correspondingly high guarantee voltages is an essential task.

One of the problems to be solved by the present invention is to improve the room temperature dielectric constant of the dielectric layer of ceramic electronic components.

One of the problems that the present invention aims to solve is to minimize the dielectric loss (DF, Dissipation Factor) of the dielectric layer of ceramic electronic components.

One of the problems that the present invention aims to solve is to improve the temperature-capacitance characteristics (TCC, Temperature Coefficient of Capacitance) of ceramic electronic components.

One of the problems to be solved by the present invention is to improve the high-temperature insulation resistance of ceramic electronic components.

One of the problems that the present invention aims to solve is to improve the mean time to failure (MTTF) of ceramic electronic components.

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

A ceramic electronic component according to an embodiment of the present invention includes a body including a dielectric layer and internal electrodes alternately disposed with the dielectric layer; and an external electrode disposed on the body; The dielectric layer includes a first region extending from the interface with the internal electrode to 50 nm in the inner direction of the dielectric layer and a second region excluding the first region, and oxygen in the first region is The average In content compared to all elements except oxygen may be 0.5 at% or more and 2.0 at% or less, and the average Sn content compared to all elements excluding oxygen may be 0.5 at% or more and 1.75 at% or less.

The method of manufacturing a ceramic electronic component according to an embodiment of the present invention includes dielectric powder as a main ingredient, Sn is contained in an amount of 0.9 mole or more and 1.8 mole or less, and In is contained in an amount of 0.05 mole or more and 0.1 mole or less relative to 100 moles of the main ingredient. preparing a dielectric composition comprising; forming a laminate by printing a conductive paste for internal electrodes on the ceramic green sheet and then laminating it; Forming a body including a dielectric layer and an internal electrode by sintering the laminate; and forming external electrodes on the body; may include.

One of the many effects of the present invention is to improve the room temperature dielectric constant of the dielectric layer of ceramic electronic components.

One of the many effects of the present invention is to minimize the dielectric loss (DF, Dissipation Factor) of the dielectric layer of ceramic electronic components.

One of the many effects of the present invention is to improve the temperature-capacitance characteristics (TCC, Temperature Coefficient of Capacitance) of ceramic electronic components.

One of the many effects of the present invention is to improve the high-temperature insulation resistance of ceramic electronic components.

One of the many effects of the present invention is to improve the mean time to failure (MTTF) of ceramic electronic components.

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

1 is a perspective view schematically showing a ceramic electronic component according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view taken along line II′ of FIG. 1.
FIG. 3 is a cross-sectional view taken along line II-II′ of FIG. 2.
Figure 4 is an exploded perspective view showing the body according to an embodiment of the present invention.
Figure 5 is a schematic diagram showing an enlarged area A of Figure 2.
Figure 6 shows the results of line profile analysis in which the contents of Ni, In, and Sn elements were measured using STEM-EDS along the regions corresponding to the p, q, and r regions of Figure 5 in the ceramic electronic component according to the comparative example. It's a graph.
FIG. 7 is a graph showing the results of line profile analysis in which the contents of Ni, In, and Sn elements were measured using STEM-EDS in the p and r regions of FIG. 5 in a ceramic electronic component according to an embodiment.
FIG. 8 is a graph showing the results of line profile analysis in which the contents of In and Sn elements were measured using STEM-EDS in the q region of FIG. 5 in a ceramic electronic component according to an embodiment.
Figure 9 is a flowchart showing the sequence of a method for manufacturing a ceramic electronic component according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described with reference to specific embodiments and attached drawings. However, the embodiments of the present invention may be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Additionally, embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art. Accordingly, the shapes and sizes of elements in the drawings may be exaggerated for clearer explanation, and elements indicated by the same symbol in the drawings are the same element.

In order to clearly explain the present invention in the drawings, parts unrelated to the description are omitted, and the size and thickness of each component shown in the drawings are arbitrarily shown for convenience of explanation, so the present invention is not necessarily limited to what is shown. . Additionally, components with the same function within the same scope are described using the same reference numerals. Furthermore, throughout the specification, when a part is said to “include” a certain element, this means that it may further include other elements rather than excluding other elements, unless specifically stated to the contrary.

In the drawing, the first direction may be defined as the stacking direction or thickness (T) direction, the second direction may be defined as the length (L) direction, and the third direction may be defined as the width (W) direction.

ceramic electronic components

1 is a perspective view schematically showing a ceramic electronic component according to an embodiment of the present invention.

FIG. 2 is a cross-sectional view taken along line II′ of FIG. 1.

FIG. 3 is a cross-sectional view taken along line II-II′ of FIG. 2.

Figure 4 is an exploded perspective view showing an exploded body according to an embodiment of the present invention.

Figure 5 is a schematic diagram showing an enlarged area A of Figure 2.

Figure 6 shows the results of line profile analysis in which the contents of Ni, In, and Sn elements were measured using STEM-EDS along the regions corresponding to the p, q, and r regions of Figure 5 in the ceramic electronic component according to the comparative example. It's a graph.

FIG. 7 is a graph showing the results of line profile analysis in which the contents of Ni, In, and Sn elements were measured using STEM-EDS in the p and r regions of FIG. 5 in a ceramic electronic component according to an embodiment.

FIG. 8 is a graph showing the results of a line profile analysis in which the content of In and Sn elements was measured using STEM-EDS in the q region of FIG. 5 in a ceramic electronic component according to an embodiment.

Hereinafter, with reference to FIGS. 1 to 8 , the ceramic electronic component 100 according to an embodiment of the present invention will be described in detail. However, although a multilayer ceramic capacitor is described as an example of a ceramic electronic component, the present invention may also be applied to various electronic products using dielectric compositions, such as inductors, piezoelectric elements, varistors, or thermistors.

A ceramic electronic component 100 according to an embodiment of the present invention includes a body 110 including a dielectric layer 111 and internal electrodes 121 and 122 alternately disposed with the dielectric layer 111, and a body 110 disposed on the body. external electrodes (131, 132); Includes, the dielectric layer includes a first region extending from the interface IF with the internal electrode to 50 nm in the inner direction of the dielectric layer, and a second region R2 excluding the first region R1, , the average content of In relative to all elements excluding oxygen in the first region may be 0.5 at% to 2.0 at%, and the average content of Sn relative to all elements excluding oxygen may be 0.5 at% to 1.75 at%.

The body 110 includes dielectric layers 111 and internal electrodes alternately disposed.

There is no particular limitation on the specific shape of the body 110, but as shown, the body 110 may have a hexahedral shape or a similar shape. Due to shrinkage of the ceramic powder included in the body 110 during the firing process, the body 110 may not have a hexahedral shape with completely straight lines, but may have a substantially hexahedral shape.

The body 110 has first and second surfaces 1 and 2 facing each other in a first direction, third and third surfaces connected to the first and second surfaces 1 and 2 and facing each other in a second direction. 4 sides (3, 4), connected to the first and second sides (1, 2), connected to the 3rd and 4th sides (3, 4), and 5th and 6th sides facing each other in the third direction ( 5, 6). The plurality of dielectric layers 111 forming the body 110 are in a fired state, and the boundaries between adjacent dielectric layers 111 may be integrated to the extent that it is difficult to check without using a scanning electron microscope (SEM). there is.

According to one embodiment of the present invention, the main component of the dielectric composition forming the dielectric layer 111 is not particularly limited as long as sufficient capacitance can be obtained. For example, barium titanate-based materials, lead composite perovskite-based materials, or strontium titanate-based materials can be used. The barium titanate-based material may include BaTiO ₃ -based ceramic powder. An example of the ceramic powder is BaTiO ₃ , BaTiO ₃ in which Ca (calcium), Zr (zirconium), etc. are partially dissolved (Ba _1-x Ca). _x )TiO ₃ (0<x<1), Ba(Ti _1-y Ca _y )O ₃ (0<y<1), (Ba _1-x Ca _x )(Ti _1-y Zr _y )O ₃ ( Examples include 0<x<1, 0<y<1) or Ba(Ti _1-y Zr _y )O ₃ (0<y<1).

In addition, the dielectric composition forming the dielectric layer 111 may contain a main component such as barium titanate (BaTiO ₃ ) and various ceramic additives, organic solvents, binders, dispersants, auxiliary components, etc. may be added according to the purpose of the present invention. In one embodiment, the dielectric layer 111 may include Sn and In. The method of including Sn and In in the dielectric layer 111 is not particularly limited, but the dielectric layer 111 can be made to include Sn and In by including a material containing Sn and In in a dielectric composition to be described later.

In one embodiment of the present invention, the electrostatic capacity characteristics, temperature-capacitance characteristics, and high-temperature reliability of the ceramic electronic component 100 are improved by not only ensuring that the dielectric layer 111 includes Sn and In, but also by controlling the concentration and distribution. One or more of these can be improved.

Meanwhile, the average thickness (t) of the dielectric layer 111 does not need to be particularly limited.

For example, it may be 10 μm or less. Additionally, the average thickness of the dielectric layer 111 can be arbitrarily set depending on desired characteristics or purposes. For example, in the case of high-voltage electronic components, the average thickness of the dielectric layer 111 may be 2.8 ㎛ or less, and in the case of small IT electronic components, the average thickness of the dielectric layer 111 may be 0.35 ㎛ to achieve miniaturization and high capacity. It may be ㎛ or less, but the present invention is not limited thereto.

However, if the average thickness (td) of the dielectric layer 111 is too thick, it may be difficult to improve the capacitance of the ceramic electronic component 100, and if it is too thin, the first region of the dielectric layer 111 as in one embodiment of the present invention. It may not be easy to control Sn and In to be distributed at a specific concentration in (R1).

In one embodiment, by adjusting the average thickness (td) of the dielectric layer 111 to 1.8 μm or more and 2.8 μm or less, the effects of improving capacitance characteristics, temperature-capacitance characteristics, and high-temperature reliability of ceramic electronic components may become more significant.

The average thickness (td) of the dielectric layer 111 may mean the average size of the dielectric layer 111 disposed between the first and second internal electrodes 121 and 122 in the first direction. Meanwhile, when the body 110 includes a plurality of dielectric layers 111, the average thickness (td) of the dielectric layers 111 may mean the average thickness of at least one of the plurality of dielectric layers 111.

The average thickness of the dielectric layer 111 can be measured by scanning an image of a cross-section in the length and thickness direction (L-T) of the body 110 with a scanning electron microscope (SEM) at 10,000 magnification. More specifically, the average value can be measured by measuring the thickness of one dielectric layer in a scanned image at 30 points at equal intervals in the length direction. The 30 equally spaced points may be designated in the capacitance forming portion (Ac). Additionally, if this average value measurement is expanded to 10 dielectric layers and the average value is measured, the average thickness of the dielectric layer can be further generalized.

The body 110 is disposed inside the body 110 and includes a first internal electrode 121 and a second internal electrode 122 arranged to face each other with the dielectric layer 111 interposed thereto, thereby forming a capacitance. It may include a capacitance forming portion (Ac) and cover portions 112 and 113 formed above and below the capacitance forming portion (Ac) in the first direction.

In addition, the capacitance forming part (Ac) is a part that contributes to forming the capacitance of the capacitor, and can be formed by repeatedly stacking a plurality of first and second internal electrodes 121 and 122 with the dielectric layer 111 interposed therebetween. there is.

Cover portions 112 and 113 may be disposed on one side and the other side of the capacitance forming portion Ac in the first direction.

The cover parts 112 and 113 include an upper cover part 112 disposed above the capacity forming portion Ac in the first direction and a lower cover portion 113 disposed below the capacity forming portion Ac in the first direction. ) may include.

The upper cover part 112 and the lower cover part 113 can be formed by stacking a single dielectric layer or two or more dielectric layers on the upper and lower surfaces of the capacitance forming part Ac in the thickness direction, respectively, and are basically resistant to physical or chemical stress. It can play a role in preventing damage to the internal electrode.

The upper cover part 112 and the lower cover part 113 do not include internal electrodes and may include the same material as the dielectric layer 111.

That is, the upper cover part 112 and the lower cover part 113 may include a ceramic material, for example, a barium titanate (BaTiO ₃ )-based ceramic material.

There is no need to specifically limit the thickness of the cover portions 112 and 113. However, in order to miniaturize and increase capacity of ceramic electronic components, the average thickness of the cover parts 112 and 113 may be 100 ㎛ or less, 30 ㎛ or less, or 20 ㎛ or less. Here, the average thickness of the cover parts 112 and 113 may mean the average thickness of each of the first cover part 112 and the second cover part 113.

The average thickness (tc) of the cover parts (112, 113) may mean the size in the first direction, and the cover parts (112, 113) measured at five points at equal intervals from the top or bottom of the capacitance forming part (Ac) ) may be the average value of the size in the first direction.

Additionally, margin portions 114 and 115 may be disposed on one side and the other side of the capacitance forming portion Ac.

The margin portions 114 and 115 may include a first margin portion 114 disposed on the fifth side 5 of the body 110 and a second margin portion 115 disposed on the sixth side 6. there is. That is, the margin portions 114 and 115 may be disposed on both end surfaces of the ceramic body 110 in the width direction.

As shown in FIG. 3, the margin portions 114 and 115 are the first and second internal electrodes 121 and 122 in a cross-section of the body 110 in the width-thickness (W-T) direction. It may refer to the area between both ends of and the boundary surface of the body 110.

The margin portions 114 and 115 may basically serve to prevent damage to the internal electrodes due to physical or chemical stress.

The margin portions 114 and 115 may be formed by forming internal electrodes by applying conductive paste on a ceramic green sheet except for areas where the margin portion is to be formed.

Additionally, in order to suppress steps caused by the internal electrodes 121 and 122, after lamination, the internal electrodes are cut to expose the fifth and sixth surfaces 5 and 6 of the body, and then a single dielectric layer or two or more dielectric layers are formed. The margin portions 114 and 115 may be formed by stacking on both sides of the capacitance forming portion Ac in the third direction (width direction).

The average width of the margin portions 114 and 115 does not need to be particularly limited. However, in order to miniaturize and increase capacity of ceramic electronic components, the average width of the margin portions 114 and 115 may be 100 ㎛ or less, 20 ㎛ or less, or 15 ㎛ or less.

The average width of the margin portions 114 and 115 may mean the average size in the third direction of the area where the internal electrode is spaced apart from the fifth surface and the average size in the third direction of the area where the internal electrode is spaced apart from the sixth surface, It may be an average value of the third direction sizes of the margin portions 114 and 115 measured at five points at equal intervals on the side of the capacitance forming portion Ac.

The internal electrodes 121 and 122 may include first and second internal electrodes 121 and 122. The first and second internal electrodes 121 and 122 are alternately disposed to face each other with the dielectric layer 111 constituting the body 110 interposed, and are disposed on the third and fourth sides 3 and 4 of the body 110. ) can be exposed respectively.

The first internal electrode 121 is spaced apart from the fourth surface 4 and exposed through the third surface 3, and the second internal electrode 122 is spaced apart from the third surface 3 and exposed through the fourth surface 4. ) can be exposed through. A first external electrode 131 is disposed on the third side 3 of the body and connected to the first internal electrode 121, and a second external electrode 132 is disposed on the fourth side 4 of the body. 2 may be connected to the internal electrode 122.

That is, the first internal electrode 121 is not connected to the second external electrode 132 but is connected to the first external electrode 131, and the second internal electrode 122 is not connected to the first external electrode 131. It is not connected but is connected to the second external electrode 132. Accordingly, the first internal electrode 121 may be formed at a certain distance apart from the fourth surface 4, and the second internal electrode 122 may be formed at a certain distance apart from the third surface 3. Additionally, the first and second internal electrodes 121 and 122 may be arranged to be spaced apart from the fifth and sixth surfaces of the body 110.

At this time, the first and second internal electrodes 121 and 122 may be electrically separated from each other by the dielectric layer 111 disposed in the middle.

The body 110 can be formed by alternately stacking ceramic green sheets on which the first internal electrode 121 is printed and ceramic green sheets on which the second internal electrode 122 is printed, and then firing them.

The material forming the internal electrodes 121 and 122 is not particularly limited, and any material with excellent electrical conductivity can be used. For example, the internal electrodes 121 and 122 include nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), gold (Au), platinum (Pt), tungsten (W), and titanium (Ti). ), aluminum (Al), and their alloys. However, the method of manufacturing the ceramic electronic component 100 according to an embodiment of the present invention includes Sn and In at a specific concentration in the dielectric composition, and Sn and In are concentrated in the first region R1 of the dielectric layer 111. Because of the distribution, it is preferable that the internal electrodes 121 and 122 do not substantially contain Sn and In.

In addition, the internal electrodes 121 and 122 include nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), gold (Au), platinum (Pt), tungsten (W), titanium (Ti), A conductive paste for internal electrodes containing at least one of aluminum (Al) and its alloys may be printed on a ceramic green sheet. The printing method for the conductive paste for internal electrodes may be a screen printing method or a gravure printing method, but the present invention is not limited thereto.

The average thickness (te) of the internal electrodes 121 and 122 does not need to be particularly limited, but may be, for example, 3 μm or less. Additionally, the average thickness of the internal electrodes 121 and 122 can be arbitrarily set depending on desired characteristics or purposes. For example, in the case of high-voltage electronic components, the average thickness of the internal electrodes 121 and 122 may be less than 1 ㎛, and in the case of small IT electronic components, the internal electrodes 121 and 122 are used to achieve miniaturization and high capacity. ) may have an average thickness of 0.35 ㎛ or less, but the present invention is not limited thereto.

The average thickness (te) of at least one of the plurality of internal electrodes 121 and 122 may mean the average size of the internal electrodes 121 and 122 in the first direction.

The average thickness of the internal electrodes 121 and 122 can be measured by scanning the image of the longitudinal and thickness direction (L-T) cross-section of the body 110 with a scanning electron microscope (SEM) at 10,000 magnification. More specifically, the average value can be measured by measuring the thickness of one internal electrode at 30 equally spaced points along the length of the scanned image. The 30 equally spaced points may be designated in the capacitance forming portion (Ac). Additionally, if this average value measurement is expanded to 10 internal electrodes and the average value is measured, the average thickness of the internal electrodes can be further generalized.

External electrodes 131 and 132 are disposed on the body 110. Specifically, the external electrodes 131 and 132 may be disposed on the third surface 3 and the fourth surface 4 of the body 110.

The external electrodes 131 and 132 are disposed on the third and fourth surfaces 3 and 4 of the body 110, respectively, and are connected to the first and second internal electrodes 121 and 122, respectively. It may include electrodes 131 and 132.

In this embodiment, a structure in which the ceramic electronic component 100 has two external electrodes 131 and 132 is described, but the number and shape of the external electrodes 131 and 132 are determined by the shape of the internal electrodes 121 and 122. It may change depending on other purposes.

On the other hand, the external electrodes 131 and 132 can be formed using any material as long as it has electrical conductivity, such as metal, and the specific material can be determined considering electrical characteristics, structural stability, etc., and can further have a multi-layer structure. there is.

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

For a more specific example of the electrode layer, the electrode layer may be a firing electrode containing a conductive metal and glass, or a resin-based electrode containing a conductive metal and resin.

Additionally, the electrode layer may be in the form of a fired electrode and a resin-based electrode sequentially formed on the body. Additionally, the electrode layer may be formed by transferring a sheet containing a conductive metal onto a body, or may be formed by transferring a sheet containing a conductive metal onto a fired electrode.

As the conductive metal included in the electrode layer, any material with excellent electrical conductivity can be used and is not particularly limited. For example, the conductive metal may be one or more of nickel (Ni), copper (Cu), and their alloys.

The plating layer plays a role in improving mounting characteristics. The type of the plating layer is not particularly limited, and may be a plating layer containing one or more of Ni, Sn, Pd, and alloys thereof, and may be formed of multiple layers.

For a more specific example of the plating layer, the plating layer may be a Ni plating layer or a Sn plating layer, and may be a form in which a Ni plating layer and a Sn plating layer are formed sequentially on an electrode layer, and a Sn plating layer, a Ni plating layer, and a Sn plating layer are formed sequentially. It can be. Additionally, the plating layer may include a plurality of Ni plating layers and/or a plurality of Sn plating layers.

The size of the ceramic electronic component 100 is not particularly limited. In an embodiment to be described later, a sample of a ceramic electronic component with a size of 3.2 mm × 1.6 mm was manufactured, but the embodiment and various embodiments of the present invention can be similarly applied to ceramic electronic components of a size larger or smaller than this.

The dielectric layer 111 of the ceramic electronic component 100 according to an embodiment of the present invention has a first region (up to 50 nm) from the interface (IF) with the internal electrodes 121 and 122 to the inside of the dielectric layer 111. R1) and a second region (R2) excluding the first region (R1), and the average content of In compared to all elements excluding oxygen in the first region is 0.5 at% or more and 2.0 at% or less, and oxygen The average Sn content compared to all elements excluded is 0.5 at% or more and 1.75 at% or less.

In the past, attempts were made to add rare earth or transition metals to the dielectric layer as a method to improve the reliability and capacitance characteristics of ceramic electronic components, and attempts were also made to add volatile metal elements to the Ni internal electrode. However, these methods have limitations in securing the desired capacitance characteristics, high-temperature reliability, and temperature-capacitance characteristics at the same time because they must take into account various variables such as controlling the type and content of additive elements, firing atmosphere, and microstructure after firing. there is.

Accordingly, in the present invention, In and Sn are added as main additives to the dielectric layer and adjusted to have a specific distribution at the interface with the internal electrode, thereby improving the electrostatic capacity characteristics, temperature-capacitance characteristics (TCC), and temperature coefficient of capacitance of ceramic electronic components. and high temperature reliability.

Meanwhile, in this specification, the room temperature dielectric constant and dielectric loss (DF, Dissipation Factor) values of the dielectric layer 111 are used as characteristics related to capacitance, and the high temperature insulation resistance and mean time to failure (MTTF) values are used as high temperature reliability and It was viewed as a related characteristic.

Referring to FIG. 5, in the ceramic electronic component 100 according to an embodiment of the present invention, the dielectric layer 111 extends from the interface IF with the internal electrodes 121 and 122 to 50 nm in the inner direction of the dielectric layer 111. It can be divided into a first area (R1), which is an area of , and a second area (R2), which is an area excluding the first area.

The dielectric layer 111 and the internal electrodes 121 and 122 form a ceramic green sheet, which will be described later, and the conductive paste for internal electrodes is printed on the ceramic green sheet and then stacked to form a laminate, and then subjected to a firing process. An interface can be formed. The interface (IF) with the internal electrodes 121 and 122 of the dielectric layer 111 can be defined as a point where the content of elements contained in the dielectric layer 111 and the internal electrodes 121 and 122 changes rapidly. Specifically, in one embodiment, the area where the Ni content compared to all elements excluding oxygen is 90 at% or more is regarded as the internal electrodes 121, 122, and the point where the Ni content compared to all elements excluding oxygen begins to decrease to 90 at% or less. Can be defined as the interface (IF) of the dielectric layer 111 with the internal electrodes 121 and 122. However, there may be a section between the dielectric layer 111 and the internal electrodes 121 and 122 where the content of Ni relative to all elements excluding oxygen decreases to 90 at% or less and continuously decreases. Accordingly, the first region R1 of the dielectric layer 111 and the internal electrodes 121 and 122 defined in one embodiment of the present invention has a Ni content of 90 at% or less compared to all elements excluding oxygen from the interface IF. It is an area that continuously decreases as it decreases, and can be seen as an area of 50 nm from the interface (IF) toward the inside of the dielectric layer 111.

FIG. 6 shows Ni, In and Ni using STEM-EDS (Scanning Transmission Electron Microscopy-Energy Dispersive This is a graph showing the results of Line Profile analysis measuring the content of Sn element.

The comparative example according to FIG. 6 corresponds to a case of a ceramic electronic component in which ITO (Indium Tin Oxide) is not added to the dielectric composition, and the dielectric layer does not substantially contain In and Sn. That is, the contents of In and Sn compared to all elements excluding oxygen detected in the dielectric layer of the ceramic electronic component according to the comparative example are each less than 0.5 at%, which can be seen as a case where the dielectric layer does not substantially contain In and Sn.

In one embodiment according to the present invention, the average content of Sn and In included in the first region R1 is the internal electrodes 121 and 122 of the dielectric layer 111 in the graph showing the results of the line profile analysis according to FIG. 7. It can be measured by calculating the average value of the contents of In and Sn from the interface (IF, horizontal axis value = 0) to 50 nm in the inner direction of the dielectric layer (horizontal value = 50 nm).

Line profile analysis according to FIG. 7 can be performed in the p, q, and r areas shown in FIG. 5. Specifically, the p area and r area may be set as areas near the interface between the internal electrodes 121 and 122 and the dielectric layer 111, and the q area may be set as the central area of the dielectric layer. At this time, the p area and r area are horizontal length=250nm 250nm area, q area is horizontal length=300nm It can be set to 300nm area. Meanwhile, the p, q and r regions do not necessarily need to be located on a straight line in the second direction.

In addition, the graph showing the results of the Line Profile analysis according to FIG. 7 calculates and shows the ratio of the contents of Ni, In, and Sn compared to the contents of all elements excluding the oxygen (O) element among the elements detected through STEM-EDS.

In addition, the average value of In and Sn contents can be further generalized by setting a plurality of p and r regions respectively, performing line profile analysis, and taking the average value. Specifically, after polishing the ceramic electronic component 100 to the center in the third direction to expose the cross sections in the first and second directions, the dielectric layer 111 and the internal electrodes 121 and 122 located in the center of the capacitance forming portion (Ac) In the area of , a plurality of p and r areas can be set and the average value of the contents of Ni, In, and Sn calculated through STEM-EDS Line Profile analysis can be taken.

In addition, in one embodiment of the present invention, the average value of the In content compared to all elements excluding oxygen and the Sn content compared to all elements excluding oxygen is the dielectric layer 111 located in the center of the capacitance forming portion Ac and the internal electrode ( In addition to the areas of 121 and 122), it can be further generalized by dividing the capacity forming part (Ac) into three parts in the first direction, dividing it into an upper part, a central part, and a lower part, and then measuring the average content of each element in the same way in the upper and lower parts. there is.

Meanwhile, the components that make up the dielectric composition forming the dielectric layer 111 may be in the form of oxides in the dielectric composition state, so in the dielectric layer 111 after firing, in addition to metal elements such as In and Sn, oxygen (O) elements may be detected. . Meanwhile, the internal electrodes 121 and 122 also contain metal elements such as Ni, rare earth elements, and additives due to oxygen contained in the dielectric layer 111 diffusing toward the internal electrode or oxide-type components added in the state before firing the internal electrode. In addition to these elements, the element oxygen (O) can be detected. The contents (at%) of In, Sn, and various additive elements described in the present invention were set as the content (at%) of the corresponding elements compared to all elements excluding oxygen.

Referring to FIG. 6, in the case of the comparative example, it is possible to specify the point where the Ni content starts to decrease below 90 at% compared to all elements excluding oxygen. However, the content of In compared to all elements excluding oxygen and the content of Sn compared to all elements excluding oxygen measured in the area from the point where the content of Ni compared to all elements excluding oxygen begins to fall below 90 at% to 50 nm towards the dielectric layer. It can be confirmed that it is measured as a noise level of less than 0.5at%.

On the other hand, referring to FIG. 7, in the first region R1 extending up to 50 nm in the direction inside the dielectric layer from the interface IF with the internal electrodes 121 and 122 of the dielectric layer 111 according to the embodiment, oxygen is excluded. It can be seen that the average content of In compared to all elements is 0.5 at% to 2.0 at%, and the average content of Sn compared to all elements excluding oxygen is 0.5 at% to 1.75 at%.

In addition, the content of In and Sn contained in the first region (R1) at a point 50 nm in the direction inside the dielectric layer from the interface (IF) with the internal electrodes 121 and 122 of the dielectric layer 111 is in the second region (R2) or It can be confirmed that the In and Sn contents are greater than those contained in the internal electrodes 121 and 122. That is, in one embodiment, In and Sn may be concentratedly distributed in the first region R1.

When In and Sn elements are concentrated and distributed near the interface between the dielectric layer 111 and the internal electrodes 121 and 122, the reliability of the ceramic electronic component 100 can be improved. However, if In and Sn elements diffuse excessively toward the internal electrode or into the interior of the dielectric layer 111, there is a risk that electrostatic capacity characteristics may deteriorate or temperature-capacitance characteristics and high-temperature reliability may deteriorate. Accordingly, in the present invention, In and Sn are included near the interface between the dielectric layer 111 and the internal electrodes 121 and 122 to improve high-temperature reliability, while In and Sn are not included in the internal electrodes 121 and 122 or the dielectric layer ( 111) By suppressing excessive internal diffusion, one or more of excellent electrostatic capacity characteristics and temperature-capacitance characteristics can be improved.

As in one embodiment of the present invention, the average content of In compared to all elements excluding oxygen in the first region (R1) is 0.5 at% or more and 2.0 at% or less, and the average content of Sn compared to all elements excluding oxygen is 0.5 at% or more and 1.75 at%. When adjusted to at% or less, In and Sn are concentrated at the interface between the dielectric layer 111 and the internal electrodes 121 and 122 toward the dielectric layer 111, causing In and Sn to diffuse to the internal electrode and reduce electrostatic capacity. phenomenon can be suppressed. In addition, In and Sn are concentrated in the first region (R1), which is an area of up to 50 nm from the interface (IF) with the internal electrodes (121, 122) of the dielectric layer (111) in the direction inside the dielectric layer. Excessive diffusion of In and Sn into the interior of the dielectric layer 111 such as region R2 can also be suppressed.

That is, as in one embodiment of the present invention, the average In content compared to all elements excluding oxygen in the first region (R1) is 0.5 at% or more and 2.0 at% or less, and the average Sn content compared to all elements excluding oxygen is 0.5 at%. If it is 1.75 at% or less, high-temperature reliability such as mean time to failure (MTTF) and high-temperature insulation resistance (IR) of the ceramic electronic component 100 can be improved, and the capacitance at room temperature and temperature-capacitance characteristics such as temperature change characteristics (TCC, Temperature Coefficient of Capacitance) can be improved.

More specifically, in one embodiment of the present invention, in the ceramic electronic component 100, the average content of In relative to all elements excluding oxygen in the first region R1 is 0.5 at% or more and 2.0 at% or less, and the total In content excluding oxygen is 0.5 at% or more. The average Sn content compared to the element is adjusted to be between 0.5 at% and 1.75 at%, so that the dielectric constant is over 2500, the MTTF is over 200 hours, the high-temperature IR value is over 1.0E+07 Ω, and the TCC is maintained in the temperature range of -55℃ to 125℃. The rate of change may satisfy one or more characteristics of -22% or more and 22% or less, and more preferably, a dielectric constant of 2500 or more, an MTTF of 200 hours or more, a high-temperature IR value of 1.0E+07 Ω or more, and -55°C to 125°C. In the temperature range, the TCC change rate can satisfy one or more characteristics of -22% or more and 22% or less.

A method of manufacturing the product so that the average In content in the first region (R1) is 0.5 at% or more and 2.0 at% or less compared to all elements except oxygen, and the Sn average content compared to all elements except oxygen is 0.5 at% or more and 1.75 at% or less. Although not particularly limited, the content of In and Sn added to the dielectric layer, the form of addition of In and Sn, the firing temperature, and the firing temperature, such as the method of manufacturing a ceramic electronic component according to an embodiment of the present invention and various embodiments thereof, which will be described later, are not particularly limited. The composition, content, and distribution of In and Sn in the first region can be determined by controlling one or more of the atmosphere and the type and content of sub-component elements of the dielectric composition.

In one embodiment, the average content of In compared to all elements excluding oxygen in the first region (R1) is I1, the average content of In compared to all elements excluding oxygen in the second region (R2) is I2, and the average content of In compared to all elements excluding oxygen in the first region (R1) is I1. ), the average content of Sn relative to all elements excluding oxygen is S1, and the average content of Sn relative to all elements excluding oxygen in the second region (R2) is S2, I1>I2 and S1>S2 can be satisfied. Accordingly, by adjusting the Sn and In contents contained in the first region (R1) of the dielectric layer 111 to be higher than the second region (R2) of the dielectric layer 111, excellent electrostatic capacity characteristics, high temperature reliability, and temperature-capacitance characteristics are achieved. It can be secured.

In one embodiment, when the average content of In compared to all elements excluding oxygen of the internal electrode is I3 and the average content of Sn compared to all elements excluding oxygen of the internal electrode is S3, I1>I2>I3 and S1>S2>S3 It is desirable to be satisfied. Accordingly, not only can excellent high-temperature reliability and temperature-capacitance characteristics be secured by ensuring that In and Sn are more concentrated in the first region (R1) of the dielectric layer 111, but also In and Sn are formed on the internal electrodes 121 and 122. ) or diffusion into the second region (R2), thereby suppressing a decrease in electrostatic capacity or a decrease in insulation resistance value.

At this time, the absolute values of I1 to I3 and S1 to S3 are the size of the ceramic electronic component 100, the content of Sn and In added to the dielectric composition forming the dielectric layer 111, the addition type of In and Sn, the firing temperature, It can be controlled by adjusting one or more of the firing atmosphere and the type and content of accessory elements of the dielectric composition.

Referring to FIG. 8, when the q area of FIG. 5 is analyzed through Line Profile through STEM-EDS, the average content of In compared to all elements excluding oxygen and the average content of Sn compared to all elements excluding oxygen are each less than 1.0 at%. You can check it. When line profile analysis is repeatedly performed in an arbitrary q area to take the average value of each element content, I2 may be 1.0 at% or less, and S2 may be 1.0 at% or less.

Meanwhile, referring to FIG. 7, the average content of In and Sn of the internal electrode is less than that of the first region or the second region, and the average content of In compared to all elements excluding oxygen and the average content of Sn compared to all elements excluding oxygen of the internal electrode The content may be less than 0.5 at% each. That is, in one embodiment, I3 may be less than 0.5 at% and S3 may be less than 0.5 at%. Here, the value “less than 0.5 at%” may mean a value corresponding to the noise level in the results measured by STEM-EDS, so it can be seen that the internal electrode does not substantially contain Sn and In.

The average content of In relative to all elements excluding oxygen (I3) of the internal electrode and the average content of Sn relative to all elements excluding oxygen (S3) do not exceed the interface (IF) with the internal electrodes 121 and 122 of the dielectric layer 111. Any area within the internal electrode that is not covered can be measured by analyzing the line profile using STEM-EDS. By performing these measurements in multiple areas on multiple internal electrodes and then taking the average value, the average content of In compared to all elements excluding oxygen (I3) and the average content of Sn compared to all elements excluding oxygen (S3) can be more generalized. there is. Specifically, after polishing the ceramic electronic component 100 to the center in the third direction to expose the cross sections in the first and second directions, the capacitance forming portion Ac is divided into three parts in the first direction and divided into an upper part, a central part, and a lower part. It can then be measured by taking the average value of the In content compared to all elements excluding oxygen and the Sn content compared to all elements excluding oxygen of the internal electrodes disposed at the top, center, and bottom.

Meanwhile, among the internal electrodes 121 and 122, the interface between the dielectric layer 111 and the internal electrodes 121 and 122, the first region of the dielectric layer 111, and the second region of the dielectric layer 111, the first region of the dielectric layer 111 In area 1, there may be a peak value where the In content compared to all elements excluding oxygen and the Sn content compared to all elements excluding oxygen are maximum. If there is a peak value in which the content of In and Sn is the maximum compared to all elements except oxygen in the first region, it can be seen that In and Sn are concentrated in the first region. From the viewpoint of securing excellent high-temperature reliability and temperature-capacitance characteristics and preventing deterioration of capacitance, the peak value of In content compared to all elements excluding oxygen in the first region is 1.2 at% or more, and Sn content compared to all elements excluding oxygen It is preferable that the peak value of is 1.0 at% or more, but is not limited thereto.

As described above, the dielectric layer 111 may be formed of a dielectric composition containing barium titanate (BaTiO ₃ ) as a main component. Accordingly, the dielectric layer 111 in the fired state may include Ba and Ti as main components, and Sn and In may be added according to an embodiment of the present invention. However, since the firing of the dielectric layer 111 is carried out in a reducing atmosphere as will be described later, it must have appropriate reduction resistance, and there is a need to improve various characteristics such as withstand voltage characteristics and high-temperature reliability of the ceramic electronic component 100, so the dielectric layer (111) may contain various secondary elements in addition to the main element.

In one embodiment, the dielectric layer includes one or more of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn as a first accessory element, and the content of the first accessory element compared to all elements excluding oxygen is 0 at%. The excess may be less than 0.6at%.

The first sub-component element is a valence-variable acceptor element and may play a role in lowering the firing temperature of the dielectric layer 111 and improving high-temperature reliability. At this time, if the content of the first sub-component element is 0 at% compared to all elements excluding oxygen, the effect of improving the dielectric constant cannot be achieved, and if it exceeds 0.6 at% compared to all elements excluding oxygen, the ceramic electronic component (100) The high-temperature reliability and temperature-capacity characteristics may be deteriorated. Therefore, it is possible to improve the electrostatic capacity of the ceramic electronic component 100 by improving the dielectric constant by adjusting the content of the first accessory element to more than 0 at% and less than 0.6 at% compared to all elements excluding oxygen contained in the dielectric layer 111. In addition, excellent high-temperature reliability and temperature-capacity characteristics can be secured.

In one embodiment, the dielectric layer includes Mg as a second accessory element, and the content of the second accessory element relative to all elements excluding oxygen may be 0.3 at% or more and 0.6 at% or less.

The second accessory element may play a role in suppressing grain growth of the dielectric contained in the dielectric layer 111 and providing reduction resistance during a firing process in a reducing atmosphere. Accordingly, the high-temperature reliability and temperature-capacitance characteristics of ceramic electronic components can be improved by including the second accessory element in the dielectric layer 111.

However, if the content of the second accessory element is less than 0.3 at% compared to all elements excluding oxygen, high-temperature reliability and temperature-capacity characteristics cannot be sufficiently improved due to excessive grain growth of the dielectric layer 111, and compared to all elements excluding oxygen, If the content of the second accessory element exceeds 0.6 at%, the dielectric constant may decrease due to excessive grain growth of the dielectric layer 111. Therefore, by controlling the content of the second accessory element to 0.3 at% or more and 0.6 at% or less compared to all elements excluding oxygen, not only can the capacitance of the ceramic electronic component 100 be improved, but also excellent high-temperature reliability and temperature- Capacity characteristics can be secured.

In one embodiment, the dielectric layer includes one or more of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb as a third accessory element, compared to all elements except oxygen. The content of the third accessory element may be 0.6 at% or more and 1.8 at% or less. Accordingly, not only can the capacitance of the ceramic electronic component 100 be improved, but also excellent high-temperature reliability and temperature-capacitance characteristics can be secured.

The third sub-component element is a rare earth element (RE) and can play a role in improving HALT reliability and dielectric constant. However, the effect according to the present invention may be more significant when the dielectric layer 111 contains two or more elements than when the dielectric layer 111 contains only one of the third subcomponent elements. In particular, the dielectric layer 111 contains Dy and Tb at the same time. It is more desirable to include

In one embodiment, the dielectric layer includes Si as a fourth sub-component element, and the content of the fourth sub-component element relative to all elements excluding oxygen may be 1.0 at% or more and 2.0 at% or less.

The fourth subcomponent element may play a role in controlling the degree of diffusion of the first to third subcomponent elements. If the content of the fourth subcomponent element compared to all elements excluding oxygen is less than 1.0 at%, it may be difficult to obtain the effect according to the present invention because the third subcomponent, which has a significant impact on reliability, does not diffuse well. On the other hand, if the content of the fourth accessory element exceeds 2.0 at% compared to all elements excluding oxygen, it may be difficult to secure sufficient dielectric constant and MTTF.

Therefore, by controlling the content of the fourth accessory element to 1.0 at% or more and 2.0 at% or less compared to all elements excluding oxygen, not only can the capacitance of the ceramic electronic component 100 be improved, but also excellent high-temperature reliability and temperature- Capacity characteristics can be secured.

Additionally, the quantitative content of each element included in the first to fourth subcomponents included in the dielectric layer 111 can be measured using a destruction method. Specifically, the measurement method using the destructive method is to crush the ceramic electronic component, remove the internal electrode, select the dielectric part, and then analyze the selected dielectric using an inductively coupled plasma spectroscopy (ICP-OES: Inductively Coupled Plasma-Optical Emission Spectroscopy). , the components of the dielectric can be quantitatively analyzed using devices such as inductively coupled plasma-mass spectrometry (ICP-MS).

When analyzing the quantitative content of elements included in the first to fourth subcomponents of the dielectric layer 111, the inductively coupled plasma analysis may be difficult due to the low sensitivity of oxygen (O) element. Accordingly, in the present invention, the content (at%) of the element included in the first to fourth subcomponents included in the dielectric layer 111 is set to the content (at%) of the element compared to all elements excluding oxygen.

Manufacturing method of ceramic electronic components

Figure 9 is a flowchart showing the sequence of a method for manufacturing a ceramic electronic component according to an embodiment of the present invention.

As shown in FIG. 9, the method of manufacturing a ceramic electronic component according to an embodiment of the present invention includes dielectric powder as a main component, and contains 0.9 mole or more and 1.8 mole or less of Sn based on 100 moles of the main component, and 0.05 mole or more of In. Preparing a dielectric composition containing 0.1 mol or less (P1); Forming a ceramic green sheet using the dielectric composition (P2); forming a laminate by printing a conductive paste for internal electrodes on the ceramic green sheet and then laminating it (P3); Forming a body including a dielectric layer and an internal electrode by sintering the laminate (P4); and forming external electrodes on the body (P5); Includes.

(P1: Step of preparing dielectric composition)

In the step (P1) of preparing the dielectric composition, a dielectric composition containing dielectric powder as the main ingredient, 0.9 mole to 1.8 mole of Sn relative to 100 moles of the main ingredient, and 0.05 mole to 0.1 mole of In is prepared. do.

The dielectric composition includes dielectric powder as a main component.

The dielectric powder _is BaTiO ₃ -based ceramic powder or ₍ Ba _{1 -x Ca} Ca _y )O ₃ (0<y<1), (Ba _1-x Ca _x )(Ti _1-y Zr _y )O ₃ (0<x<1, 0<y<1) or Ba(Ti _{1- y} Zr _y )O ₃ (0<y<1), etc.

In addition to the main components, the dielectric composition preferably contains 0.9 mole to 1.8 mole of Sn and 0.05 mole to 0.1 mole of In based on 100 moles of the main component.

The content of Sn and In in the dielectric composition may be a variable that controls the distribution of Sn and In in the dielectric layer 111 of the ceramic electronic component 100. If the content of Sn and In exceeds the above range, the MTTF value of the ceramic electronic component 100 may decrease or the X7S characteristic may not be satisfied, and may be included in the first region R1 of the dielectric layer 111 of the present invention. The average In content is 0.5 at% or more and 2.0 at% or less, and the Sn average content may be difficult to control to be 0.5 at% or more and 1.75 at% or less.

The form in which Sn and In contained in the dielectric composition are added is not particularly limited. For example, Sn oxide and In oxide may be mixed at a certain ratio and added to the dielectric composition. However, when Sn and In are added to the dielectric composition in the form of indium tin oxide (ITO), the reliability improvement effect of the ceramic electronic component 100 according to the present invention can be further improved.

Indium tin oxide (ITO) is a material that contains indium oxide (In ₂ O ₃ -) and tin oxide (SnO ₂ ) mixed in a certain ratio. In one embodiment, indium tin oxide consisting of In: 74wt%, O: 18wt%, and Sn: 8wt% was added to the dielectric composition, but the amount is not limited thereto, and the amount can be adjusted even if indium tin oxide having a different composition is added. Thus, the concentration of Sn and In in the dielectric composition can be adjusted.

Meanwhile, according to one embodiment, when indium tin oxide composed of In: 74wt%, O: 18wt%, and Sn: 8wt% is added to the dielectric composition, the content of the indium tin compound contained in the dielectric composition is 0.5 mole compared to 100 moles of the main component. It is preferable that the mole is greater than or equal to 1.0 mole in terms of improving the reliability of the ceramic electronic component 100.

In one embodiment, the dielectric composition may include a first subcomponent including one or more of an oxide or a carbonate of a variable-valence acceptor element.

The elements included in the first subcomponent may play a role in lowering the firing temperature of the dielectric layer 111 and improving high-temperature reliability. At this time, the valence variable acceptor element may mean one or more of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn.

If the content of the first subcomponent is less than 0.1 mole compared to 100 mole of the main component, it is difficult to improve the dielectric constant of the dielectric layer 111, and if the content of the first subcomponent exceeds 0.3 mole compared to 100 mole of the main component, the high temperature reliability of the ceramic electronic component 100 And temperature-capacity characteristics may deteriorate.

Therefore, when the dielectric composition contains the first subcomponent in an amount of 0.1 mole or more and 0.3 mole or less relative to 100 moles of the main component, not only can the electrostatic capacity of the ceramic electronic component 100 be improved, but also excellent high temperature reliability and temperature-capacitance characteristics. can be secured.

Meanwhile, in the ceramic electronic component 100 after firing, the content of the first accessory element relative to all elements excluding oxygen included in the dielectric layer 111 may be greater than 0 at% and less than or equal to 0.6 at%.

In one embodiment, the dielectric composition may include a second subcomponent including one or more of an oxide or carbonate of Mg.

The element included in the second subcomponent may play a role in suppressing grain growth of the dielectric included in the dielectric layer 111 and providing reduction resistance during the firing process in a reducing atmosphere.

If the content of the second subcomponent is less than 0.3 mole compared to 100 mole of the main component, high temperature reliability and temperature-capacitance characteristics cannot be sufficiently improved due to excessive grain growth of the dielectric layer 111, and the content of the second subcomponent is 0.9 mole compared to 100 mole of the main component. If it exceeds this, the dielectric constant may decrease due to excessive grain growth of the dielectric layer 111.

Therefore, when the dielectric composition contains the second subcomponent in an amount of 0.3 mole or more and 0.9 mole or less relative to 100 moles of the main component, not only can the capacitance of the ceramic electronic component 100 be improved, but also excellent high-temperature reliability and temperature-capacitance characteristics can be secured.

Meanwhile, in the ceramic electronic component 100 after firing, the content of the second accessory element relative to all elements excluding oxygen included in the dielectric layer 111 may be 0.3 at% or more and 0.6 at% or less.

In one embodiment, the dielectric composition may include a third subcomponent comprising one or more of oxides and carbonates of rare earth elements.

The third subcomponent may play a role in improving high-temperature reliability and dielectric constant of the dielectric layer. At this time, the rare earth element may be one or more of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb.

In one embodiment, the dielectric composition not only improves the capacitance of the ceramic electronic component 100 by including 0.3 mole or more and 0.9 mole or less of the third subcomponent relative to 100 moles of the main component, but also provides excellent high-temperature reliability and temperature-capacitance. characteristics can be secured.

Meanwhile, in the ceramic electronic component 100 after firing, the content of the third accessory element relative to all elements excluding oxygen included in the dielectric layer 111 may be 0.6 at% or more and 1.8 at% or less.

Meanwhile, it is more effective in improving the reliability of the ceramic electronic component 100 when the dielectric layer 111 contains an oxide or carbonate containing two or more of the rare earth elements than when it contains only one of the third sub-component elements.

For example, adding Tb ₄ O ₇ and Dy ₂ O ₃ at the same time improves the dielectric constant of the ceramic electronic component 100 compared to adding only Tb ₄ O ₇ or only Dy ₂ O ₃ as the third subcomponent. It is more advantageous for improving electrostatic capacity, high temperature reliability, and temperature-capacitance characteristics.

More specifically, when Tb ₄ O ₇ alone is added as a third subcomponent to the dielectric composition in an amount of 0.6 mol or more relative to 100 mol of the main component, high temperature insulation resistance and MTTF value may decrease. In addition, when 0.6 mol or more of only Dy ₂ O ₃ is added as the third subcomponent, characteristics such as temperature-capacitance characteristics and high-temperature reliability are improved, but there is a possibility that the dielectric constant may decrease.

Therefore, when the dielectric composition simultaneously contains Tb ₄ O ₇ and Dy ₂ O ₃ as the third subcomponent, the content of Tb ₄ O ₇ is 0.1 mole or more and 0.4 mole or less relative to 100 moles of the main ingredient, and the content of Dy ₂ O ₃ is the content of the main ingredient. It is preferable that it is 0.2 mol or more and 0.5 mol or less per 100 mol.

In one embodiment, the dielectric composition may include a fourth subcomponent including one or more of an oxide of Si, a carbonate of Si, and a glass containing Si.

The elements included in the fourth subcomponent may play a role in controlling the degree of diffusion of the first to third subcomponent elements in the dielectric layer 111.

If the content of the fourth subcomponent is less than 1.0 mole compared to 100 mole of the main ingredient, it may be difficult to obtain the effect according to the present invention because the third subcomponent, which has a significant impact on reliability, does not diffuse well, and the content of the fourth subcomponent is 2.0 mole compared to 100 mole of the main ingredient. If the molar value is exceeded, it may be difficult to secure sufficient dielectric constant and MTTF.

Therefore, the dielectric composition not only improves the capacitance of the ceramic electronic component 100 by containing the fourth subcomponent in an amount of 1.0 mol to 2.0 mol based on 100 mol of the main component, but also provides excellent high-temperature reliability and temperature-capacitance characteristics. It can be secured.

(P2: Step of forming ceramic green sheet)

A ceramic green sheet can be formed using the dielectric composition.

The dielectric composition may be prepared into a slurry by mixing with a binder and milling before being formed into a ceramic green sheet. The slurry prepared in this way can be manufactured into a ceramic green sheet using a sheet manufacturing molding machine.

Meanwhile, the ceramic green sheet may be manufactured separately into a ceramic green sheet for the capacity forming portion (Ac) and a ceramic green sheet for the cover portions (112, 113). The composition of the ceramic green sheet for the capacitance forming portion (Ac) and the ceramic green sheet for the cover portions 112 and 113 may be substantially the same, but each function of the cover portions 112 and 113 and the capacitance forming portion (Ac) may be different from each other. It can be prepared in different compositions to achieve this.

(P3: Step of forming a laminate)

Afterwards, conductive paste for internal electrodes is printed on the ceramic green sheet.

The conductive paste for the internal electrode is nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), gold (Au), platinum (Pt), tin (Sn), tungsten (W), and titanium (Ti). ), it may be a paste containing one or more of indium (In), aluminum (Al), and alloys thereof.

The conductive paste for the internal electrode may be formed on the ceramic green sheet and spaced apart at regular intervals. That is, the conductive paste for internal electrodes may be striped.

Thereafter, a laminate may be formed by stacking a plurality of ceramic green sheets on which the conductive paste for internal electrodes is printed.

In the process of forming a laminate, a pressed bar can be manufactured by pressing and stacking a plurality of ceramic green sheets printed with the conductive paste for internal electrodes, and cutting the pressed bar to an appropriate size using a cutter. A laminate may be formed.

(P4: Step of forming the body)

Thereafter, the fabricated laminate is fired to form a body 110 including a dielectric layer 111 and internal electrodes 121 and 122.

In one embodiment, a plasticizing process may be performed on the laminate before the firing, and after the plasticizing, the laminate is heated at 1150 to 1200°C in a reducing atmosphere of 0.1%H ₂ / 99.9%N ₂ to 0.5%H ₂ / 99.5%N _{2 .} Firing can proceed by maintaining the temperature for 2 hours.

In one embodiment, after the firing process, a re-oxidation process may be further included in an N ₂ atmosphere at 1040° C. for 3 hours.

In the process of firing the body 110, the dielectric layer 111 may also be fired. At this time, the concentration distribution of Sn and In contained in the dielectric layer 111 may vary depending on the firing atmosphere. That is, the firing atmosphere of the body 110 can be another variable that controls the distribution of Sn and In in the dielectric layer 111.

In a firing atmosphere where the hydrogen concentration is lowered, In and Sn contained in the dielectric composition are dispersed and the dielectric constant and DF level of the dielectric layer 111 can be improved, but temperature-capacitance characteristics and high-temperature reliability are improved due to non-uniform grain growth. It can be difficult to do.

Therefore, in one embodiment, the electrostatic capacity characteristics, temperature-capacitance characteristics, and high-temperature reliability of the ceramic electronic component 100 can be improved by performing the firing in an atmosphere of 730 mV or more and 760 mV or less EMF. At this time, when converting the EMF in the above range to hydrogen concentration, the firing is preferably performed in an atmosphere with a hydrogen concentration of 0.2 vol% or more and 0.4 vol% or less. Meanwhile, the electromotive force (EMF) value may vary depending on the hydrogen concentration and the temperature of the measuring sensor, and the EMF value in the present invention may correspond to a value measured at a sensor temperature of 850°C.

(P5: Step of forming external electrode)

Afterwards, external electrodes 131 and 132 are formed on the body 110 formed by firing the laminate.

The external electrodes 131 and 132 may be formed on the fired body 110 using a conductive paste for external electrodes through a termination process and a firing process. However, in addition to using a conductive paste for external electrodes, the external electrode can also be formed by a wet plating method such as electrolytic plating or electroless plating, or a dry plating method such as sputtering.

Hereinafter, the effects of the ceramic electronic component and the method for manufacturing the ceramic electronic component according to an embodiment of the present invention will be described through various examples.

Samples of the ceramic electronic components used in each example were manufactured as follows, and the contents of ITO and the first to fourth subcomponents listed in Tables 1 to 6 were calculated as the number of moles of the corresponding components relative to 100 moles of the main component. In addition, the ITO added in each example used Indium Tin Oxide consisting of In: 74wt%, O: 18wt%, and Sn: 8wt%.

(Samples of ceramic electronic components)

BaTiO ₃ powder with an average particle size of 100 nm was used as the dielectric main component base material. Zirconia beads were used as mixing/dispersing media, and ITO (Indium-Tin-Oxide, In: 74wt%, O: 18wt% Sn: 8wt%) and minor components corresponding to the compositions specified in Tables 1 to 6 below were used. The raw material powder and the main ingredient BaTiO ₃ powder were mixed with an ethanol/toluene solvent and a dispersant and milled for 10 hours. The binder was mixed and milled for an additional 10 hours. The slurry prepared in this way was used to manufacture a ceramic green sheet for the cover and capacity forming part with a thickness of 5.0 ㎛ using a sheet manufacturing molding machine. Ni internal electrodes were printed on the ceramic green sheet for the capacitance forming part. The upper and lower covers were manufactured by laminating 25 layers of ceramic green sheets for the cover, and 20 layers of printed ceramic green sheets for the capacitance forming part were stacked while pressing to produce a bar. The bar is cut to 3.2mm using a cutter. It was cut into 1.6mm-sized laminates. The manufactured laminate is plasticized and then heated at a temperature of 1150 to 1200°C in a reducing atmosphere of 0.1% H ₂ / 99.9% N ₂ ~ 0.5 % H ₂ / 99.5% N ₂ (H ₂ O/H ₂ /N ₂ atmosphere). After firing under conditions of holding time for 2 hours, the body 110 was manufactured by re-oxidation at 1040°C in N2 atmosphere for 3 hours. Here, 0.1% hydrogen concentration corresponds to the condition of electromotive force of 680mV in the oxygen partial pressure meter, and 0.5% hydrogen concentration corresponds to the condition of electromotive force of 760mV. The external electrodes 131 and 132 were completed through a termination process and electrode firing using Cu paste for the fired body 110. Accordingly, a sample of a 3.2mm × 1.6mm ceramic electronic component with a dielectric thickness of approximately 2.2μm or less after firing and a number of dielectric layers of 20 was produced.

Additionally, in each example, the firing atmosphere may vary depending on the hydrogen concentration, and the EMF value in each firing atmosphere is a value measured at a sensor temperature of 850°C using a thermoelectric type hydrogen sensor.

ITO detection was determined by line profile analysis of the area (first area and second area) adjacent to the internal electrodes 121 and 122 among the dielectric layer 111 of the ceramic electronic component using STEM-EDS along the second direction. ), the case where the sum of the In content compared to all elements excluding oxygen and the Sn content compared to all elements excluding oxygen exceeds 0.5 at% is indicated as ○, and the case where it is less than 0.5 at% is indicated as X.

The dielectric constant at room temperature was determined by measuring the capacitance of the sample under the conditions of 1 kHz and AC 0.5V/μm using an LCR meter, and then measuring the relative permittivity of the dielectric layer based on the thickness of the dielectric layer, the area of the internal electrode, and the number of layers. was created, and a value of 2500 or more was set as the target characteristic.

The DF (Dissipation Factor) value was also measured using an LCR meter under the conditions of 1 kHz and AC 0.5V/μm, and a value of 10% or less was set as the target characteristic.

The change in capacitance (TCC) according to temperature was measured by applying 0.1Vrms in the temperature range of -55℃ to 125℃, and the change in capacitance was more than -22% and less than 22% in the temperature range of -55℃ to 125℃. (hereinafter referred to as “X7S characteristics”) was set as the target characteristic.

The high-temperature IR value was taken as the average value by measuring the insulation resistance (IR) value after charging for 60 seconds by applying DC 10V/μm voltage at a temperature of 150℃ to 10 samples, and the value was more than 1.0E+07Ω. was set as the target characteristic.

The MTTF (Mean Time To Failure) value was created by measuring the time for failure by applying a voltage equivalent to an electric field of 40 V/μm at 150°C to 40 samples and measuring the average time. A value of 200 hours or more is the target characteristic. It was done as follows.

(Example 1)

Test numbers 1-1 to 1-4, 2-1 to 2-4, and 3-1 to 3-4 in Table 1 represent various experimental conditions in which the firing atmosphere and the content of ITO added to the dielectric composition were varied.

The characteristics of samples of ceramic electronic components manufactured according to each test number in Table 1 are listed in Table 2.

exam number Experimental conditions plastic atmosphere
EMF (mV) ITO content first subingredient Second subingredient third subingredient Fourth subingredient MnO ₂ V ₂ O ₅ MgCO ₃ Dy ₂ O ₃ Tb ₄ O ₇ SiO ₂ 1-1 745 0 0.2 0.1 0.6 0.5 0.1 1.65 1-2 745 0.5 1-3 745 One 1-4 745 1.5 2-1 715 0 2-2 715 0.5 2-3 715 One 2-4 715 1.5 3-1 685 0 3-2 685 0.5 3-3 685 One 3-4 685 1.5

sample characteristics test
number ITO
Detection room temperature
permittivity DF X7S TCC (%) High temperature
IR(Ω) MTTF(hrs) Secure target characteristics @-55℃ @125℃ 1-1 X 2749 5.9 -20.7 -14.7 1.70.E+07 176 X 1-2 O 2800 5.4 -21 -14.7 1.92.E+07 243 O 1-3 O 2817 5.4 -21.7 -15.3 1.80.E+07 232 O 1-4 O 2971 5.4 -24.6 -15.3 2.02.E+07 196 X 2-1 X 2755 6 -21.1 -18.9 1.44.E+07 118 X 2-2 O 2789 5.8 -21.3 -17.7 1.39.E+07 147 X 2-3 O 2817 5.7 -20.9 -17.1 1.64.E+07 136 X 2-4 O 2771 5.7 -23.8 -13.6 3.10.E+07 131 X 3-1 X 2948 6.2 -20.8 -24.6 1.39.E+07 67 X 3-2 O 2856 5.8 -21.7 -22.8 1.68.E+07 55 X 3-3 O 2811 5.8 -20.8 -22.1 1.55.E+06 63 X 3-4 O 2795 5.7 -21.2 -21.6 1.21.E+06 45 X

Referring to Tables 1 and 2, test numbers 1-4, 2-4, 3-1 to 3-3 have a dielectric constant of 2500 or more and a DF value of 10% or less, but do not satisfy the X7S characteristic due to uneven grain growth. You can confirm that this is not the case.

It can be confirmed that test numbers 2-1 to 2-4 and 3-1 to 3-2 have MTTF values lower than 200 hours.

In the case of test numbers 1-2 and 1-3, it can be confirmed that the MTTF value is more than 200 hours, the dielectric constant is more than 2500, the high temperature IR value is more than 1.0E+0.7Ω, and the X7R characteristics are all satisfied. Test numbers 1-2 and 2-3 are cases where the amount of ITO added is 0.5 or 1.0 mole compared to 100 mole of the main component in the firing atmosphere EMF 730~760 mV (hydrogen concentration ~0.4%), and after manufacturing the sample, the dielectric layer 111 and the internal electrode The average content of In relative to all elements excluding oxygen in the first region (R1) from the interface of (121, 122) to 50 nm in the inner direction of the dielectric layer 111 is 0.5 at% or more and 2.0 at% or less, and the total content excluding oxygen is 0.5 at% or more and 2.0 at% or less. The average Sn content compared to the element is 0.5 at% or more and 1.75 at% or less.

Referring to Test No. 1-4, when the ITO content increases to 1.5 moles compared to 100 moles of the main component, the average content of In compared to all elements excluding oxygen in the first region (R1) after sample production and compared to all elements excluding oxygen Although the average content of Sn can be detected as exceeding 2at%, it can be confirmed that the MTTF value decreases to less than 200 hours and does not satisfy the X7S characteristics.

In the case of test numbers 2-2, 2-3, 2-4, 3-2, 3-3, and 3-4, the content of In compared to all elements excluding oxygen in the entire area of the dielectric layer 111 and the total elements excluding oxygen Compared to the Sn content, the sum of the contents was detected as exceeding 0.5 at%, and the dielectric constant was over 2500 and the DF level was below 10%, but test numbers 2-4, 3-2, and 3-3 satisfied the X7S characteristics. As a result, it can be confirmed that test numbers 2-2, 2-3, 2-4, 3-2, 3-3, and 3-4 do not have an MTTF of more than 200 hours.

As a result of analyzing the dielectric layer of the sample in test numbers 2-4, 3-2, and 3-3, it is expected that the reason for not satisfying the X7S characteristics is due to the uneven grain growth of the dielectric layer. As a result of analyzing the dielectric layers of the samples in 2-4, 3-2, 3-3, and 3-4, In and Sn were not distributed intensively in the first area of the dielectric layer, but were dispersed throughout the entire area of the dielectric layer, The average content of In compared to all elements excluding oxygen in the region (R1) was 0.5 at% to 2.0 at%, and the average content of Sn compared to all elements excluding oxygen did not meet the conditions of 0.5 at% to 1.75 at%.

On the other hand, in the case of test numbers 1-2 and 1-3 in which all target characteristics are satisfied, the first region (R1) extends from the interface of the dielectric layer 111 and the internal electrodes 121 and 122 to 50 nm in the inner direction of the dielectric layer 111. ), the average content of In compared to all elements excluding oxygen was confirmed to be 0.5 at% to 2.0 at%, and the average content of Sn compared to all elements excluding oxygen was confirmed to be 0.5 at% to 1.75 at%. That is, in order to satisfy all of the MTTF value of 200 hours or more, dielectric constant of 2500 or more, high-temperature IR value of 1.0E+0.7Ω or more, and X7R characteristics, a dielectric layer ( The average content of In compared to all elements excluding oxygen in the first region (R1) up to 50 nm in the inner direction of 111) is 0.5 at% or more and 2.0 at% or less, and the average content of Sn compared to all elements excluding oxygen is 0.5 at% or more. It is preferable that it is 1.75at% or less.

Meanwhile, the firing atmosphere is preferably carried out in the range of 730-760 mV (hydrogen concentration 0.2-0.4 vol%) at EMF (sensor temperature 850°C), and the content of ITO added to the dielectric composition is 0.5 mole or more and 1.0 mole per 100 mole of the main component. It is preferable that it is less than a mole.

(Example 2)

Test numbers 4-1 to 4-3, 5-1 to 5-3, 6-1 to 6-4, and 7-1 to 7-4 in Table 3 are the test numbers of the first or second subcomponents included in the dielectric composition. Various experimental conditions with different contents were prepared.

The characteristics of samples of ceramic electronic components manufactured according to each test number in Table 3 are listed in Table 4.

test
number Experimental conditions firing
atmosphere
EMF (mV) ITO content first subingredient Second subingredient third subingredient Fourth subingredient MnO ₂ V ₂ O ₅ MgCO ₃ Dy ₂ O ₃ Tb ₄ O ₇ SiO ₂ 4-1 730~760 0.5 0 0.3 0.6 0.5 0.1 1.65 4-2 0.1 0.2 4-3 0.3 0 5-1 One 0 0.3 5-2 0.1 0.2 5-3 0.3 0 6-1 730~760 0.5 0.2 0.1 0 0.5 0.1 1.65 6-2 0.3 6-3 0.9 6-4 1.2 7-1 One 0 7-2 0.3 7-3 0.9 7-4 1.2

sample characteristics test
number ITO
Detection room temperature
permittivity DF X7S TCC (%) High temperature IR(Ω) MTTF(hrs) Secure target characteristics @-55℃ @125℃ 4-1 O 2334 5.1 -20.3 -13.7 1.92.E+07 211 X 4-2 O 2514 5.3 -21.7 -15.3 1.80.E+07 257 O 4-3 O 2867 6.3 -21.2 -23.7 1.79.E+05 187 X 5-1 O 2248 5 -21.3 -13.1 1.79.E+07 197 X 5-2 O 2507 5.3 -21.9 -14.8 1.51.E+07 248 O 5-3 O 2724 6.2 -21.8 -23.1 1.50.E+07 168 X 6-1 O 3378 6.8 -24.9 -23.4 8.96.E+06 175 X 6-2 O 2936 5.8 -21.3 -18.8 1.63.E+07 237 O 6-3 O 2689 5.4 -21 -16.7 4.32.E+07 248 O 6-4 O 2487 5.3 -24.3 -19.7 1.32.E+08 197 X 7-1 O 3348 6.8 -24 -22.6 5.88.E+06 167 X 7-2 O 3914 5.8 -21.1 -16.7 1.13.E+07 224 O 7-3 O 2711 5.4 -20.5 -15.8 3.92.E+07 238 O 7-4 O 2498 5.3 -23.2 -19 2.12.E+08 184 X

Referring to Table 3 and Table 4, in test numbers 4-1 and 5-1, the content of MnO ₂ , the first subcomponent, is 0 mole compared to 100 mole of the main ingredient, and the content of V ₂ O ₅ is 0.3 mole compared to 100 mole of the main ingredient. It can be confirmed that the dielectric constant at room temperature is less than 2500.

Test numbers 4-3 and 5-3 do _{not satisfy the} You can confirm that it is.

Therefore, the content of the first subcomponent contained in the dielectric composition is preferably 0.1 mol or more and 0.3 mol or less relative to 100 moles of the main component, and the first subcomponent element in the dielectric layer 111 of the ceramic electronic component 100 is greater than 0 at% and 0.6 at%. It is preferable to include the following.

Referring to test numbers 6-1 to 6-4 and 7-1 to 7-4, it can be seen that when MgCO ₃ is included as a second subcomponent in the dielectric composition, there is an effect of improving TCC characteristics and increasing high temperature IR. However, it can be confirmed that in Test Nos. 6-4 and 7-4, where the MgCO ₃ content is 1.2 moles compared to 100 moles of the main component, the dielectric constant at room temperature is lowered to less than 2500 due to excessive grain growth suppression, and the X7S characteristics are not satisfied.

Therefore, the content of the second subcomponent included in the dielectric composition is preferably 0.3 mole or more and 0.9 mole or less relative to 100 moles of the main component, and the content of the second subcomponent element compared to all elements excluding oxygen in the dielectric layer 111 of the ceramic electronic component 100 The content is preferably 0.3 at% or more and 0.6 at% or less.

(Example 3)

Test numbers 8-1 to 8-4, 9-1 to 9-4, 10-1 to 10-3, and 11-1 to 11-3 in Table 5 are the test numbers of the third or fourth subcomponent included in the dielectric composition. Various experimental conditions with different contents were prepared.

The characteristics of samples of ceramic electronic components manufactured according to each test number in Table 5 are listed in Table 6.

test
number Experimental conditions firing
atmosphere
EMF (mV) ITO content first subingredient Second subingredient third subingredient Fourth subingredient MnO ₂ V ₂ O ₅ MgCO ₃ Dy ₂ O ₃ Tb ₄ O ₇ SiO ₂ 8-1 730~760 0.5 0.2 0.1 0.6 0 0.6 1.65 8-2 0.2 0.4 8-3 0.4 0.2 8-4 0.6 0 9-1 One 0 0.6 9-2 0.2 0.4 9-3 0.4 0.2 9-4 0.6 0 10-1 730~760 0.5 0.2 0.1 0.6 0.5 0.1 0.65 10-2 1.15 10-3 2.15 11-1 One 0.65 11-2 1.15 11-3 2.15

sample characteristics test
number ITO
Detection room temperature
permittivity DF X7S TCC (%) High temperature
IR(Ω) MTTF(hrs) Secure target characteristics @-55℃ @125℃ 8-1 O 3107 6.4 -22.8 -17.1 8.93.E+06 194 X 8-2 O 2876 5.8 -21.4 -16.6 1.52.E+07 224 O 8-3 O 2677 5.4 -20.7 -15.9 2.84.E+07 239 O 8-4 O 2468 5.3 -20.9 -15.1 3.15.E+07 217 X 9-1 O 3087 6.3 -21.4 -16.7 9.13.E+06 181 X 9-2 O 2744 5.7 -21.4 16.1 1.43.E+07 224 O 9-3 O 2616 5.4 -20.1 -15.4 2.17.E+07 219 O 9-4 O 2397 5.3 -20.1 -15.2 2.76.E+07 204 X 10-1 O 3317 6.7 -23.7 -16.8 9.42.E+06 176 X 10-2 O 3107 6.2 -22 -16.1 1.07.E+07 201 O 10-3 O 2434 5.3 -21.4 -12.4 9.98.E+07 194 X 11-1 O 3247 6.6 -22.8 -16.4 8.88.E+06 167 X 11-2 O 3087 6.3 -21.7 -15.8 1.78.E+07 214 O 11-3 O 2374 5.3 -21.1 -13.1 1.28.E+08 185 X

In Tables 5 and 6, referring to test numbers 8-1 to 8-4 and 9-1 to 9-4, when a third subcomponent, which is a rare earth oxide, is added to the dielectric composition, the MTTF value increases and the room temperature dielectric constant is It can be seen that there is an increasing effect. However, in the case of Test Nos. 8-1 and 9-1, where only 0.6 mol of Tb ₄ O ₇ is added compared to 100 mol of the main ingredient, the high temperature IR and MTTF values may decrease. also. In the case of test numbers 8-4 and 9-4, in which only 0.6 mol of Dy ₂ O ₃ is added per 100 mol of the main ingredient, the dielectric constant at room temperature may decrease.

Therefore, it is preferable that the content of the third subcomponent included in the dielectric composition is 0.3 mole or more and 0.9 mole or less based on 100 moles of the main component. In particular, rather than including only one of Tb ₄ O ₇ and Dy ₂ O ₃ as the third subcomponent, it is preferable to include a mixture of Tb ₄ O ₇ and Dy ₂ O ₃ in an appropriate amount, and the content of Tb ₄ O ₇ is 100 moles of the main component. It is more preferable that the content of Dy ₂ O ₃ is 0.2 mol or more and 0.5 mol or less relative to 100 mol of the main component. At this time, it is preferable that the content of the third sub-component element in the dielectric layer 111 of the ceramic electronic component 100 is 0.6 at% or more and 1.8 at% or less compared to all elements excluding oxygen.

Test numbers 10-1 to 10-3 and 11-1 to 11-3 are cases in which SiO- ₂ is included as the fourth subcomponent of the dielectric composition. Referring to test numbers 10-1 and 11-1, when the SiO ₂ content is 0.65 mol compared to 100 mol of the main component, it causes excessively fast grain growth and suppresses the diffusion of ITO and the third subcomponent, resulting in X7S characteristics It can be confirmed that this is not satisfied and the MTTF is less than 200 hours.

Referring to test numbers 10-3 and 11-3, it can be confirmed that the content of SiO ₂ is 2.15 moles relative to 100 moles of the main component, and the room temperature dielectric constant is less than 2500 or the MTTF is less than 200 hours.

Therefore, the content of the fourth subcomponent contained in the overall oil composition is preferably 1.0 mole or more and 2.0 mole or less relative to 100 moles of the main component, and the fourth subcomponent element relative to all elements excluding oxygen in the dielectric layer 111 of the ceramic electronic component 100 The content is preferably 1.0 at% or more and 2.0 at% or less.

Although the embodiments of the present invention have been described in detail above, the present invention is not limited by the above-described embodiments and the attached drawings, but is intended to be limited by the appended claims. Accordingly, various forms of substitution, modification, and change may be made by those skilled in the art without departing from the technical spirit of the present invention as set forth in the claims, and this also falls within the scope of the present invention. something to do.

In addition, the expression ‘one embodiment’ used in the present disclosure does not mean the same embodiment, but is provided to emphasize and explain different unique features. However, the above-presented embodiments do not exclude being implemented in combination with the features of other embodiments. For example, even if a matter described in one specific embodiment is not explained in another embodiment, it can be understood as a description related to another embodiment, unless there is a description that is contrary or contradictory to the matter in another embodiment. You can.

The terms used in this disclosure are only used to describe one embodiment and are not intended to limit the disclosure. At this time, singular expressions include plural expressions, unless the context clearly indicates otherwise.

100: Ceramic electronic components
110: body
111: dielectric layer
121, 122: internal electrode
131, 132: external electrode
R1: first region
R2: second region
IF: Interface with the internal electrode of the dielectric layer

Claims (21)

A body including a dielectric layer and internal electrodes alternately disposed with the dielectric layer; and
External electrodes disposed on the body; Including,
The dielectric layer includes a first region extending from the interface with the internal electrode to 50 nm in the inner direction of the dielectric layer and a second region excluding the first region,
In the first region, the average content of In compared to all elements excluding oxygen is 0.5 at% to 2.0 at%, and the average content of Sn compared to all elements excluding oxygen is 0.5 at% to 1.75 at%.
Ceramic electronic components.
According to paragraph 1,
The average In content compared to all elements excluding oxygen in the first region is I1, the average In content compared to all elements excluding oxygen in the second region is I2,
When the average Sn content compared to all elements excluding oxygen in the first region is S1, and the average Sn content compared to all elements excluding oxygen in the second region is S2,
Satisfies I1>I2 and S1>S2
Ceramic electronic components.
According to paragraph 2,
When the average content of In compared to all elements excluding oxygen of the internal electrode is I3, and the average content of Sn compared to all elements excluding oxygen of the internal electrode is S3,
Satisfies I1>I2>I3 and S1>S2>S3
Ceramic electronic components.
According to paragraph 3,
The I2 is 1.0 at% or less, and the S2 is 1.0 at% or less.
Ceramic electronic components.
According to clause 4,
The I3 is less than 0.5at%, and the S3 is less than 0.5at%.
Ceramic electronic components.
According to paragraph 1,
In the first region, the peak value of the In content compared to all elements excluding oxygen is 1.2 at% or more, and the peak value of the Sn content compared to all elements excluding oxygen is 1.0 at% or more.
Ceramic electronic components.
According to paragraph 1,
The internal electrode has a Ni content of more than 90 at% compared to all elements excluding oxygen, and the interface with the internal electrode of the dielectric layer is a point where the Ni content compared to all elements excluding oxygen begins to decrease below 90 at%.
Ceramic electronic components.
According to paragraph 1,
The average thickness of the dielectric layer is 1.8 μm or more and 2.8 μm or less.
Ceramic electronic components.
According to paragraph 1,
The dielectric layer contains Ba and Ti as main components.
Ceramic electronic components.
According to clause 9,
The dielectric layer contains a first accessory element including one or more of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn in an amount of more than 0 at% and less than 0.6 at% compared to all elements excluding oxygen,
Ceramic electronic components.
According to clause 9,
The dielectric layer includes Mg as a second accessory element, and the content of the second accessory element relative to all elements excluding oxygen is 0.3 at% or more and 0.6 at% or less.
Ceramic electronic components.
According to clause 9,
The dielectric layer includes one or more of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb as a third subcomponent element, and the third subcomponent compared to all elements excluding oxygen. The element content is 0.6 at% or more and 1.8 at% or less.
Ceramic electronic components.
According to clause 9,
The dielectric layer includes Si as a fourth sub-component element, and the content of the fourth sub-component element relative to all elements excluding oxygen is 1.0 at% or more and 2.0 at% or less.
Ceramic electronic components.
According to paragraph 1,
The ceramic electronic component has one or more characteristics of a dielectric constant of 2500 or more, an MTTF of 200 hours or more, a high-temperature IR value of 1.0E+07 Ω or more, and a TCC change rate of -22% or more and 22% or less in the temperature range of -55 ℃ to 125 ℃. satisfying
Ceramic electronic components.
Preparing a dielectric composition containing dielectric powder as a main component, containing 0.9 mole to 1.8 mole Sn and 0.05 mole to 0.1 mole In relative to 100 moles of the main component;
forming a ceramic green sheet using the dielectric composition;
forming a laminate by printing a conductive paste for internal electrodes on the ceramic green sheet and then laminating it;
Forming a body including a dielectric layer and an internal electrode by sintering the laminate; and
forming external electrodes on the body; containing
Manufacturing method of ceramic electronic components.
According to clause 15,
In and Sn included in the dielectric composition are contained in the form of indium tin oxide (Indium-Tin-Oxide), and the dielectric composition contains 0.5 mole or more and 1.0 mole or less of the indium tin oxide relative to 100 moles of the main component.
Manufacturing method of ceramic electronic components.
According to clause 15,
The dielectric powder is BaTiO ₃ powder.
Manufacturing method of ceramic electronic components.
According to clause 17,
The dielectric composition contains a first subcomponent containing at least one of an oxide or a carbonate of a variable valency acceptor element in an amount of 0.1 mole to 0.3 mole based on 100 moles of the main component,
The valence variable acceptor element is one or more of Mn, V, Cr, Fe, Ni, Co, Cu and Zn.
Manufacturing method of ceramic electronic components.
According to clause 17,
The dielectric composition contains 0.3 mole or more and 0.9 mole or less of a second subcomponent containing one or more of the oxide or carbonate of Mg relative to 100 mole of the main component.
Manufacturing method of ceramic electronic components.
According to clause 17,
The dielectric composition contains a third subcomponent containing at least one of oxides and carbonates of rare earth elements in an amount of 0.3 mole to 0.9 mole based on 100 moles of the main component,
The rare earth element is one or more of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd and Yb.
Manufacturing method of ceramic electronic components.
According to clause 17,
The dielectric composition contains a fourth subcomponent including one or more of Si oxide, Si carbonate, and Si-containing glass in an amount of 1.0 mol to 2.0 mol based on 100 mol of the main component.
Manufacturing method of ceramic electronic components.

Images