KR20220128973A - Dielectric composition and multilayered electronic component comprising the same - Google Patents

Abstract

One aspect of the present invention is to provide a dielectric composition with excellent reliability. The dielectric composition comprises: a main component having a perovskite structure represented by ABO_3, wherein A is at least one among Ba, Sr, and Ca, and B is at least one among Ti, Zr, and Hf; and a first sub-component, wherein the first sub-component contains 0.1 mol or more of a rare earth element, 0.02 mol or more of Nb, and 0.25 mol or more and 0.9 mol or less of Mg relative to 100 mol of the main component. A sum of the rare earth element and the Nb content is 1.5 mol or less. Another one aspect of the present invention is to provide a stacked electronic component comprising the dielectric composition.

Description

Dielectric composition and stacked electronic component comprising same

The present invention relates to a dielectric composition and a laminated electronic component comprising the same.

Multi-Layered Ceramic Capacitors (MLCCs), one of the multilayer electronic components, are used in imaging devices such as liquid crystal displays (LCDs) and plasma display panels (PDPs), computers, and smartphones. and a chip-type capacitor mounted on a printed circuit board of various electronic products, such as mobile phones, to charge or discharge electricity.

Such a multilayer ceramic capacitor may be used as a component of various electronic devices due to its small size, high capacity, and easy mounting. As various electronic devices such as computers and mobile devices are miniaturized and have high output, the demand for miniaturization and high capacity multilayer ceramic capacitors is increasing.

In order to achieve miniaturization and high capacity of the multilayer ceramic capacitor, it is necessary to increase the number of stacks by reducing the thickness of the dielectric layer and the internal electrode. At present, the thickness of the dielectric layer has reached the level of about 0.6 μm, and thinning is continuing.

However, as the thickness of the dielectric layer decreases, reliability is lowered, and characteristics such as insulation resistance and breakdown voltage are deteriorated.

In order to solve this problem, a new method for securing high reliability not only in terms of the structure of the multilayer ceramic capacitor but also in terms of the composition of the dielectric is needed.

If a dielectric composition that can increase the reliability level by one step from the current level is secured, a thinner multilayer ceramic capacitor can be manufactured.

SUMMARY OF THE INVENTION One object of the present invention is to provide a dielectric composition having excellent reliability and a multilayer electronic component including the same.

Another object of the present invention is to provide a dielectric composition having excellent insulation resistance and a multilayer electronic component including the same.

Another object of the present invention is to provide a dielectric composition having a high breakdown voltage and a multilayer electronic component including the same.

Another object of the present invention is to achieve miniaturization and high capacity of a multilayer electronic component.

One aspect of the present invention includes a main component and a first subcomponent having a perovskite structure represented by ABO ₃ (A is at least one of Ba, Sr, and Ca, and B is at least one of Ti, Zr, and Hf) , wherein the first subcomponent includes a rare earth element: 0.1 mol or more, Nb: 0.02 mol or more, and Mg: 0.25 mol or more and 0.9 mol or less, relative to 100 mol of the main component, and the sum of the rare earth element and Nb content is 1.5 mol or less. A composition is provided.

Another aspect of the present invention is a body including a dielectric layer and an internal electrode; and an external electrode disposed on the body and connected to the internal electrode, wherein the dielectric layer includes a dielectric composition, wherein the dielectric composition is ABO ₃ (A is at least one of Ba, Sr, and Ca, and B is Ti , Zr and Hf), and a main component having a perovskite structure and a first subcomponent, wherein the first subcomponent comprises 100 moles of the main component, a rare earth element: 0.1 mole or more, Nb: 0.02 mole or more and Mg: 0.25 mol or more and 0.9 mol or less, wherein the sum of the rare earth element and Nb content is 1.5 mol or less.

As one effect among various effects of the present invention, the reliability of the dielectric composition and the multilayer electronic component including the same may be improved.

However, the various and beneficial advantages and effects of the present invention are not limited to the above, and will be more easily understood in the course of describing specific embodiments of the present invention.

1 schematically illustrates a perspective view of a multilayer electronic component according to an embodiment of the present invention.
FIG. 2 schematically illustrates a cross-sectional view II′ of FIG. 1 .
FIG. 3 schematically illustrates a cross-sectional view taken along II-II′ of FIG. 1 .
4 is a graph of the harsh reliability evaluation (Halt) results for Test Nos. 1 to 3;
5 is an IV curve for Test Nos. 4 to 6;

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to specific embodiments and the accompanying drawings. However, the embodiment of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. Further, the embodiments of the present invention are provided in order 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 a clearer description, and elements indicated by the same reference numerals in the drawings are the same elements.

And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and the thickness is enlarged to clearly express various layers and regions, and components having the same function within the scope of the same idea are referred to as the same. It is explained using symbols. Furthermore, throughout the specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

In the drawings, an X direction may be defined as a second direction, an L direction or a length direction, a Y direction may be defined as a third direction, a W direction or a width direction, and a Z direction may be defined as a first direction, a stacking direction, a T direction, or a thickness direction.

dielectric composition

A dielectric composition according to an embodiment of the present invention comprises a main component and a material having a perovskite structure represented by ABO ₃ (A is at least one of Ba, Sr, and Ca, and B is at least one of Ti, Zr, and Hf) 1 subcomponent, wherein the first subcomponent contains rare earth element: 0.1 mol or more, Nb: 0.02 mol or more, and Mg: 0.25 mol or more and 0.9 mol or less, relative to 100 moles of the main component, and the sum of the rare earth element and Nb content is 1.5 moles or less.

In the case of a main component having a perovskite structure represented by ABO ₃ , an oxygen vacancy in which a site for oxygen is vacated may occur. For example, when calcining is carried out in a reducing atmosphere, oxygen vacancy may occur, and when carbon is combined with oxygen of ABO ₃ and evaporated in the form of CO ₂ by a debinder or the like, oxygen vacancy occurs. This can happen.

That is, O has a -2 valence charge. If the oxygen vacancy site is empty, oxygen vacancies with a +2-valent charge are generated. The larger the number and the higher the temperature and voltage, the higher the movement speed and amount of movement, which further deteriorates the reliability.

In order to solve this problem of oxygen vacancies, there is generally known a method of improving reliability by reducing the concentration of oxygen vacancies by adding a rare earth element.

However, the content of additives that can be dissolved in the A-site in the ABO ₃ structure is limited, and it is difficult to effectively reduce the concentration of oxygen vacancies only by adding a rare earth element, or there is a fear that the insulation resistance may be lowered due to excessive semiconductorization.

Accordingly, in the present invention, in a dielectric composition including a main component having a perovskite structure represented by ABO ₃ (A is at least one of Ba, Sr, and Ca, and B is at least one of Ti, Zr, and Hf), the first dielectric composition As subcomponents, it is intended to improve reliability by adding appropriate amounts of rare earth elements, Nb and Mg.

Hereinafter, each component of the dielectric composition according to an embodiment of the present invention will be described in detail.

a) main component

A dielectric composition according to an embodiment of the present invention includes a main component having a perovskite structure represented by ABO ₃ (A is at least one of Ba, Sr, and Ca, and B is at least one of Ti, Zr, and Hf) do.

For more specific examples of the main component having a perovskite structure represented by ABO ₃ , BaTiO ₃ , SrTiO ₃ , (Ba _1-x Ca _x )(Ti _1-y Ca _y )O ₃ (where x is 0≤x≤0.3, y is 0≤y≤0.1), (Ba _1-x Ca _x )(Ti _1-y Zr _y )O ₃ (where x is 0≤x≤0.3, y is 0≤y≤ 0.5), and Ba(Ti _1-y Zr _y )O ₃ (here, 0<y≤0.5).

The dielectric composition according to an embodiment of the present invention may have a dielectric constant at room temperature of 2000 or more.

The main component is not particularly limited, but the average particle diameter of the main component powder may be 40 nm or more and 200 nm or less.

b) the first subcomponent

According to an embodiment of the present invention, the dielectric composition contains rare earth element: 0.1 mol or more, Nb: 0.02 mol or more, and Mg: 0.25 mol or more and 0.9 mol or less, relative to 100 mol of the main component, and the rare earth element and Nb content The sum of the first subcomponents is 1.5 moles or less.

The rare earth element acts as a donor by replacing the A-site of the ABO ₃ structure, thereby reducing the concentration of oxygen vacancies and improving reliability. In addition, the rare earth element acts as a barrier that blocks the flow of electrons at the grain boundary, thereby suppressing an increase in leakage current. When the content of the rare earth element is less than 0.1 mol relative to 100 mol of the main component, the above-described effect may be insufficient.

In general, since the content of additives that can be dissolved in A-site in the ABO ₃ structure is limited, it is difficult to effectively reduce the concentration of oxygen vacancies only by adding rare earth elements, or insulation resistance may be reduced due to excessive semiconductorization.

Since the additive content that can be dissolved in the B-site is higher than the additive content that can be dissolved in the A-site in the ABO ₃ structure, in the present invention, the B-site of the ABO ₃ structure is substituted with a rare earth element to form a donor. The reliability is improved by adding Nb, which plays a role. When the Nb content is less than 0.02 mol relative to 100 mol of the main component, the above-described effect may be insufficient.

In addition, since Nb is disposed not only in dielectric grains but also at grain boundaries, it is possible to prevent a decrease in insulation resistance of the multilayer ceramic capacitor and improve reliability.

As the sum of the rare earth element and Nb content increases, it is advantageous in terms of improving reliability, but since it becomes semiconductor at a certain amount or more and deteriorates the properties of the insulator and sinterability, the sum of the rare earth element and Nb content is 1.5 moles or less compared to 100 moles of the main component. it is preferable

Mg acts as an acceptor by substituting the B-site of the ABO ₃ structure, and may serve to reduce the electron concentration.

Since Mg competitively alicyclics the B-site of the Nb and ABO ₃ structure, it is necessary to appropriately control its content.

When the Mg content is 0.25 mol or more and 0.9 mol or less compared to 100 mol of the main component, the reliability improvement effect due to n-type formation can be maximized. can't A more preferable range of the Mg content may be 0.25 mol or more and 0.7 mol or less with respect to 100 mol of the main component.

On the other hand, the rare earth element is not particularly limited, and for example, scandium (Sc), yttrium (Y), lanthanum (La), actinium (Ac), cerium (Ce), praseodymium (Pr), neodium (Nd) , Promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thulium (Tm), Ytterbium (Yb) ), and ruthenium (Lu).

However, when using a rare earth element with a larger ionic radius than Dy, for example, lantinum (La), samarium (Sm), etc., the Ba site can be replaced more effectively, so it is more effective in reducing the concentration of oxygen vacancy defects, but excessive semiconductor There is a risk that the insulation resistance will drop sharply due to heating. Accordingly, it may be more preferable that the rare earth element be an element having an ionic radius smaller than that of Dy or Dy. Examples of the rare earth element having an ionic radius smaller than that of Dy include Ho, Y, Er, and Yb.

In addition, in consideration of both reduction in oxygen vacancy defect concentration and securing insulation resistance, it may be more preferable to use BaTiO ₃ as the main component having the perovskite structure represented by ABO ₃ and Dy as the rare earth element. have.

b) second subcomponent

According to an embodiment of the present invention, the dielectric composition may include an oxide or carbonate including at least one of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn as the second subcomponent.

As the second subcomponent, an oxide or carbonate containing at least one of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn may be included in an amount of 0.1 to 2.0 moles based on 100 moles of the main component.

The second subcomponent serves to lower the firing temperature and improve high-temperature withstand voltage characteristics of the multilayer ceramic capacitor to which the dielectric composition is applied.

The content of the second subcomponent and the content of the third subcomponent, which will be described later, are amounts included with respect to 100 moles of the main component, and in particular, may be defined as moles of metal ions included in each subcomponent.

When the content of the second subcomponent is less than 0.1 mol, the sintering temperature may be increased and the high-temperature withstand voltage characteristics may be slightly deteriorated.

When the content of the second subcomponent is 2.0 mol or more, high-temperature withstand voltage characteristics and room-temperature resistivity may be deteriorated.

In particular, the dielectric composition according to an embodiment of the present invention may include the second subcomponent having a content of 0.1 to 2.0 moles based on 100 moles of the main component, whereby low temperature firing is possible and high high temperature withstand voltage characteristics can be obtained. have.

c) third subcomponent

According to an embodiment of the present invention, the dielectric composition may include an oxide including at least one of Si and Al or a glass compound including Si as the third subcomponent.

The dielectric composition may further include 0.001 to 0.5 moles of a third subcomponent, which is an oxide including at least one of Si and Al, or a glass compound including Si, based on 100 moles of the main component.

The content of the third subcomponent may be based on the content of at least one of Si and Al included in the third subcomponent without distinguishing an additive form such as glass, oxide, or carbonate.

The third subcomponent serves to lower the firing temperature and improve high-temperature withstand voltage characteristics of the multilayer ceramic capacitor to which the dielectric composition is applied.

When the content of the third subcomponent exceeds 0.5 mol with respect to 100 mol of the main component, there may be problems such as a decrease in sinterability and density, and generation of a secondary phase, which is not preferable.

In particular, according to an embodiment of the present invention, since the dielectric composition contains Al in an amount of 0.5 mol or less, Al acts as an acceptor to reduce electron concentration, thereby improving reliability.

Stacked Electronic Components

1 schematically illustrates a perspective view of a multilayer electronic component according to an embodiment of the present invention.

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

FIG. 3 schematically illustrates a cross-sectional view taken along II-II′ of FIG. 1 .

1 to 3 , a multilayer 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 ; and external electrodes 131 and 132 disposed on the body 110 and connected to the internal electrodes 121 and 122, wherein the dielectric layer 111 includes a dielectric composition, wherein the dielectric composition is ABO ₃ (A is at least one of Ba, Sr, and Ca, and B is at least one of Ti, Zr, and Hf). , rare earth element: 0.1 mol or more, Nb: 0.02 mol or more, and Mg: 0.25 mol or more and 0.9 mol or less, wherein the sum of the rare earth element and Nb content is 1.5 mol or less.

Hereinafter, portions overlapping with those described in the above-described dielectric composition will be omitted to avoid overlapping descriptions. In addition, although a multilayer ceramic capacitor will be described as an example of a multilayer electronic component, the present invention may be applied to various electronic products using the above-described dielectric composition, for example, an inductor, a piezoelectric element, a varistor, or a thermistor.

In the body 110 , a dielectric layer 111 and internal electrodes 121 and 122 are alternately stacked.

The specific shape of the body 110 is not particularly limited, but as shown, the body 110 may have a hexahedral shape or a similar shape. Due to the shrinkage of the ceramic powder included in the body 110 during the firing process, the body 110 may not have a perfectly straight hexahedral shape, but may have a substantially hexahedral shape.

The body 110 is connected to first and second surfaces 1 and 2 facing each other in a first direction (Z direction), the first and second surfaces 1 and 2, and is connected to each other in a second direction (X direction). connected to the third and fourth surfaces (3, 4), the first and second surfaces (1, 2) opposite to each other, and connected to the third and fourth surfaces (3, 4) in the third direction (Y direction) ) may have fifth and sixth surfaces 5 and 6 facing each other.

The plurality of dielectric layers 111 forming the body 110 are in a fired state, and the boundary between the adjacent dielectric layers 111 can be integrated to the extent that it is difficult to check without using a scanning electron microscope (SEM). have.

The dielectric layer 111 may be formed using the above-described dielectric composition.

The dielectric layer 111 may include a plurality of grains and grain boundaries disposed between adjacent grains.

In this case, Nb included in the dielectric composition may be included in the plurality of grains and grain boundaries. Since Nb is disposed not only in the grains but also at the grain boundaries, it is possible to prevent a decrease in insulation resistance of the multilayer ceramic capacitor and improve reliability.

In addition, the average particle diameter of the crystal grains may be 200 nm or less, and in this case, the effect of improving reliability and insulation resistance according to the present invention may be more remarkable.

On the other hand, the body 110 is disposed inside the body 110 and includes a first internal electrode 121 and a second internal electrode 122 disposed to face each other with a dielectric layer 111 interposed therebetween, and has a capacitance. It may include the formed capacitor forming part A and cover parts 112 and 113 formed on the upper and lower portions of the capacitor forming part A.

In addition, the capacitor forming part (A) is a part contributing to capacitance formation of the capacitor, and may be formed by repeatedly stacking a plurality of first and second internal electrodes 121 and 122 with a dielectric layer 111 interposed therebetween. have.

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

The upper cover part 112 and the lower cover part 113 do not include an internal electrode 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.

In addition, margin portions 114 and 115 may be disposed on a side surface of the capacity forming portion A.

The margin portions 114 and 115 include a margin portion 114 disposed on the sixth surface 6 of the body 110 and a margin portion 115 disposed on the fifth surface 5 of the body 110 . That is, the margin portions 114 and 115 may be disposed on both sides of the ceramic body 110 in the width direction.

As shown in FIG. 3 , the margin portions 114 and 115 include both ends of the first and second internal electrodes 121 and 122 and the body 110 in a cross-section cut in the width-thickness (W-T) direction. It may mean a region between the boundary surfaces of (110).

The margins 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 a conductive paste on the ceramic green sheet except where the margin portion is to be formed.

In addition, in order to suppress the step difference caused by the internal electrodes 121 and 122, after lamination, the internal electrodes are cut to be exposed to 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 laminating them on both sides of the capacitance forming portion A in the width direction.

The internal electrodes 121 and 122 are alternately stacked with the dielectric layer 111 .

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 therebetween, and the third and fourth surfaces 3 and 4 of the body 110 . ) can be exposed respectively.

Referring to FIG. 2 , 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 may be exposed through the fourth surface 4 .

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

The body 110 may be formed by alternately stacking a ceramic green sheet on which the first internal electrode 121 is printed and a ceramic green sheet on which the second internal electrode 122 is printed, followed by firing. The material for forming the internal electrodes 121 and 122 is not particularly limited, and a material having excellent electrical conductivity may be used.

For example, a conductive paste for internal electrodes including at least one of palladium (Pd), nickel (Ni), copper (Cu), and an alloy thereof may be formed by printing on a ceramic green sheet.

As the printing method of the conductive paste for internal electrodes, a screen printing method or a gravure printing method may be used, but the present invention is not limited thereto.

On the other hand, in order to achieve miniaturization and high capacity of the multilayer ceramic capacitor, it is necessary to increase the number of stacks by reducing the thickness of the dielectric layer and the internal electrode. properties may be deteriorated.

Accordingly, as the thickness of the dielectric layer and the internal electrode decreases, the reliability improvement effect according to the present invention may be increased.

In particular, when the thickness te of the internal electrodes 121 and 122 and the thickness td of the dielectric layer 111 are 0.41 μm or less, the effect of improving reliability and insulation resistance according to the present invention may be remarkable.

The thickness te of the internal electrodes 121 and 122 may mean an average thickness of the first and second internal electrodes 121 and 122 .

The thickness te of the internal electrodes 121 and 122 may be measured by scanning images of the third and first cross-sections (L-T cross-sections) of the body 110 with a scanning electron microscope (SEM).

For example, the third and first direction cross-sections (W-T cross-sections) cut in the central part of the body 110 in the second direction (L direction) are scanned with a scanning electron microscope (SEM). With respect to the internal electrodes 121 and 122 of , the thickness may be measured at 30 equal intervals in the third direction to measure the average value.

The 30 equally spaced points may be measured in the capacitor forming part A, which means a region where the internal electrodes 121 and 122 overlap each other.

The thickness td of the dielectric layer 111 may mean an average thickness of the dielectric layer 111 disposed between the first and second internal electrodes 121 and 122 .

Like the thickness te of the internal electrode, the thickness td of the dielectric layer 111 is also imaged with a scanning electron microscope (SEM) in the third and first direction cross-sections (L-T cross-sections) of the body 110. It can be measured by scanning.

For example, the third and first direction cross-sections (W-T cross-sections) cut in the central part of the body 110 in the second direction (L direction) are scanned with a scanning electron microscope (SEM). For the dielectric layer 111 of , the thickness may be measured at 30 points equally spaced in the third direction to measure the average value.

The 30 equally spaced points may be measured in the capacitor forming part A, which means a region where the internal electrodes 121 and 122 overlap each other.

In addition, the thickness of the cover parts 112 and 113 does not need to be specifically limited. However, in order to more easily achieve miniaturization and high capacity of the multilayer electronic component, the thickness tp of the cover parts 112 and 113 may be 20 μm or less.

The external electrodes 131 and 132 are disposed on the body 110 and are connected to the internal electrodes 121 and 122 .

2 , first and second respectively disposed on the third and fourth surfaces 3 and 4 of the body 110 and connected to the first and second internal electrodes 121 and 122 , respectively External electrodes 131 and 132 may be included.

In the present embodiment, a structure in which the multilayer electronic component 100 has two external electrodes 131 and 132 is described. However, the number and shape of the external electrodes 131 and 132 is determined according to the shape of the internal electrodes 121 and 122 . or for other purposes.

On the other hand, the external electrodes 131 and 132 may be formed using any material as long as they have electrical conductivity, such as metal, and specific materials may be determined in consideration of electrical characteristics and structural stability, and furthermore, may have a multilayer structure. have.

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

As a more specific example of the electrode layers 131a and 132a, the electrode layers 131a and 132a may be fired electrodes including conductive metal and glass, or resin-based electrodes including conductive metal and resin.

In addition, the electrode layers 131a and 132a may have a shape in which a fired electrode and a resin-based electrode are sequentially formed on a body. In addition, the electrode layers 131a and 132a may be formed by transferring a sheet including a conductive metal onto the body or by transferring a sheet including a conductive metal onto the firing electrode.

As the conductive metal included in the electrode layers 131a and 132a, a material having excellent electrical conductivity may be used, and the material is not particularly limited. For example, the conductive metal may be one or more of nickel (Ni), copper (Cu), and alloys thereof.

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

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

However, in order to achieve miniaturization and high capacity at the same time, the thickness of the dielectric layer and the internal electrode must be thinned to increase the number of stacks, so the present invention in a stacked electronic component having a size of 1005 (length × width, 1.0 mm × 0.5 mm) or less As a result, reliability and insulation resistance improvement effects may be more significant.

Therefore, when defining the distance between the third and fourth surfaces of the body as L and the distance between the fifth and sixth surfaces as W, the L may be 1.0 mm or less, and the W may be 0.5 mm or less. That is, it may be a stacked electronic component having a size of 1005 (length × width, 1.0 mm × 0.5 mm) or less.

(Example)

In an embodiment of the present invention, additives such as Dy, Nb, and Mg, binders, and organic solvents such as ethanol are added to barium titanate (BaTiO ₃ ) powder, which is a main component, and wet mixed to prepare a dielectric slurry, and then the dielectric slurry is transferred to a carrier. A ceramic green sheet is prepared by coating and drying on a film, thereby forming a dielectric layer.

The ceramic green sheet may be prepared as a slurry by mixing ceramic powder, a binder, and a solvent, and the slurry may be prepared in a sheet type having a thickness of several μm by a doctor blade method.

Next, a conductive paste for internal electrodes having an average nickel particle size of 0.1 to 0.2 μm and containing 40 to 50 parts by weight of nickel powder may be prepared.

After forming an internal electrode by applying the conductive paste for internal electrode on the green sheet by a screen printing method, the green sheet on which the internal electrode pattern is disposed was laminated to form a laminate, and then the laminate was compressed and cut. .

Thereafter, the cut laminate was heated to remove the binder, and then fired in a high temperature reducing atmosphere to form a ceramic body.

In the calcination process, after calcining for 2 hours at a temperature of 1100 to 1200 ° C in a reducing atmosphere (0.1% H ₂ /99.9% N ₂ , H ₂ O/H ₂ /N ₂ atmosphere), nitrogen (N ₂ ) at 1000 ° C. Heat treatment was performed by re-oxidation in an atmosphere for 3 hours.

Next, the external electrode was completed through a termination process and electrode firing with copper (Cu) paste for the fired ceramic body.

In addition, the dielectric layer 111 and the internal electrodes 121 and 122 inside the ceramic body 110 were manufactured to have an average thickness of 0.4 μm or less after firing.

(Example 1)

First, in order to confirm the effect of the sum of Dy and Nb contents on reliability, the sum of Dy and Nb contents compared to 100 moles of the main component was 1.5 moles (Test No. 1) and 1.8 moles (Test No. 2) in the above-mentioned manufacturing process. , Test Nos. 1 to 3 were prepared so as to be 2.1 moles (Test No. 3).

Severe reliability evaluation (Halt) was performed on Test Nos. 1 to 3, which are prototype multilayer ceramic capacitor (Proto-type MLCC) specimens completed as described above.

4 is a graph of harsh reliability evaluation (Halt) results for Test Nos. 1 to 3; Severe reliability evaluation is to measure the change in insulation resistance by applying 1.5 times the reference voltage at 125°C for 12 hours.

4(a) is the case of Test No. 1, and it can be seen that the sum of Dy and Nb contents is 1.5 mol compared to 100 mol of the main component, and there is no defect in the severe reliability evaluation, so it can be seen that the reliability is excellent.

In the case of Test No. 1, it can be seen that the nominal capacity is 101% and the breakdown voltage (BDV) is 63V, which is excellent in reliability evaluation in terms of capacity and BDV.

Figure 4(b) is the case of Test No. 2, in which the sum of Dy and Nb contents is 1.8 moles relative to 100 moles of the main component, and Fig. 4(c) shows that the sum of Dy and Nb contents is 2.1 moles compared to 100 moles of Ti among the main components. This is the case of Test No. 3 with the addition of

In the case of Test Nos. 2 and 3, a decrease in reliability was confirmed as a large number of defects occurred in the severe reliability evaluation.

In addition, in the case of Test No. 2, the nominal capacity is 90%, the breakdown voltage (BDV) is 58V, and in the case of Test No. 3, the nominal capacity is 82%, and the breakdown voltage (BDV) is is 47V, indicating that all of them fall short of the standard.

Therefore, when the sum of Dy and Nb contents exceeds 1.5 mol relative to 100 mol of Ti among the main components, reliability is deteriorated, and it can be confirmed that it is difficult to secure capacity due to lack of sinterability.

(Example 2)

In order to confirm the electrical characteristics according to the change in the Mg content, Test Nos. 4 to 6 were prepared so that Dy, Nb, and Mg had the contents shown in Table 1 below relative to 100 moles of Ti among the main components through the above-described manufacturing process.

The capacity, DF (dissipation factor), and BDV (breaking down voltage) were measured for Test Nos. 4 to 6, which are prototype multilayer ceramic capacitor (Proto-type MLCC) specimens completed as described above, and the following table 1 is described.

5 is an I-V curve for Test Nos. 4 to 6, FIG. 5(a) is an I-V curve for Test No. 4, FIG. 5(b) is an I-V curve for Test No. 5, and FIG. 5(c) is This is the I-V curve for Test No. 6.

test number Dy (mole) Nb (mol) Mg (mol) Capacity (μF) DF(%) BDV(V) 4 0.9 0.05 0.467 4.91 3.3 78 5 0.9 0.05 0.7 5.25 3.5 72 6 0.9 0.05 0.93 5.17 3.5 58

As can be seen in Table 1, FIGS. 5 (a) and 5 (b), Test Nos. 4 and 5 are cases in which the Mg content satisfies 0.25 mol or more and 0.9 mol or less relative to 100 mol of the main component, and the capacity and loss factor and It was confirmed that all of the BDV characteristics were excellent. In addition, it can be seen that Test Nos. 4 and 5 have higher BDV values than Test Nos. 1 to 3 in which Mg is not added.

However, in the case of Test No. 6 in which Mg was added in excess, as can be seen in Table 1 and FIG. 5(c), it can be seen that the Mg content exceeds 0.9 mol relative to 100 mol of the main component, resulting in a sharp decrease in BDV. In addition, it can be seen that the capacity is also lower than Test No. 5 in which the Mg content is 0.7 mol relative to 100 mol of the main component.

Although embodiments of the present invention have been described in detail above, the present invention is not limited by the above-described embodiments and the accompanying drawings, but is intended to be limited by the appended claims. Therefore, various types of substitution, modification and change will be possible by those skilled in the art within the scope not departing from the technical spirit of the present invention described in the claims, and it is also said that it falls within the scope of the present invention. something to do.

100: stacked electronic component
110: body
121, 122: internal electrode
111: dielectric layer
112, 113: cover part
114, 115: margin part
131, 132: external electrode

Claims (7)

a body including a dielectric layer and an internal electrode; and
and an external electrode disposed on the body and connected to the internal electrode;
The dielectric layer comprises a dielectric composition,
The dielectric composition comprises a main component and a first subcomponent having a perovskite structure represented by ABO ₃ (A is at least one of Ba, Sr and Ca, and B is at least one of Ti, Zr and Hf),
The first subcomponent includes a rare earth element: 0.1 mol or more, Nb: 0.02 mol or more, and Mg: 0.25 mol or more and 0.9 mol or less, relative to 100 mol of the main component, and the sum of the rare earth element and Nb content is 1.5 mol or less,
The rare earth element is at least one selected from Ho, Y, Er, Yb and Dy, and the average thickness of the dielectric layer is 0.41 μm or less, and the average thickness of the internal electrode is 0.41 μm or less.
Stacked electronic components.
According to claim 1,
The Mg is 0.25 mol or more and 0.7 mol or less compared to 100 mol of the main component
Stacked electronic components.
According to claim 1,
The dielectric composition comprises 0.1 to 2.0 moles of a second subcomponent, which is an oxide or carbonate containing at least one of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn, based on 100 moles of the main component.
Stacked electronic components.
According to claim 1,
The dielectric composition contains 0.001 to 0.5 moles of a third subcomponent, which is an oxide containing at least one of Si and Al, or a glass compound containing Si, based on 100 moles of the main component.
Stacked electronic components.
According to claim 1,
The size of the stacked electronic component is 1005 (length × width, 1.0 mm × 0.5 mm) or less.
Stacked electronic components.
3. The method of claim 2,
The dielectric composition comprises 0.1 to 2.0 moles of a second subcomponent, which is an oxide or carbonate containing at least one of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn, based on 100 moles of the main component.
Stacked electronic components.
7. The method of claim 6,
The dielectric composition contains 0.001 to 0.5 moles of a third subcomponent, which is an oxide containing at least one of Si and Al, or a glass compound containing Si, based on 100 moles of the main component.
Stacked electronic components.

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