Dielectrics and multilayer ceramic electronic components containing them

Abstract

To provide dielectric material and a multilayer ceramic electronic component having a high dielectric constant and excellent withstanding voltage characteristics.SOLUTION: An dielectric according to one embodiment of the invention includes: a main component represented by (Ba1-XCaX)(Ti1-y(Zr,Sn,Hf)y)O3 (wherein 0≤X≤1, 0≤y≤0.5); a first subcomponent including one or more of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Nb, Tb, Eu, Tm, La, Lu and Yb; a second sub-component including Si and / or Al; and a third sub-component including Ba and / or Ca.SELECTED DRAWING: Figure 4

Description

Technical Field

[0001] The present invention relates to a dielectric and a multilayer ceramic electronic component including the same.

Background Art

[0002] In recent years, along with the trend of miniaturization of electronic products, miniaturization and large capacity have also been demanded for multilayer ceramic electronic components. In response to the requirements for miniaturization and large capacity of multilayer ceramic electronic components, the dielectric sheets of multilayer ceramic electronic components have also been thinned.

[0003] On the other hand, it is known that the withstand voltage characteristics and the like of electronic components are greatly affected by the fine structure inside the components. Due to the thinning of the dielectric sheet, the size of the crystal grains and the distribution of components in the dielectric layer are affected, and there is a problem that the withstand voltage and reliability characteristics of the chip deteriorate. Generally, since the grain boundaries between the crystal grains of electronic components have high-resistance components, research has been conducted to provide highly reliable electronic components by increasing the ratio of the grain boundaries inside the dielectric layer.

[0004] However, the problem that the reliability, high-temperature withstand voltage characteristics, and dc-bias characteristics of the product deteriorate due to the thinning of the dielectric layer due to the ultra-miniaturization / high capacity of electronic components still exists. In addition, there is an increasing demand for characteristics that prevent the deterioration of reliability and the like as described above and realize a high effective dielectric constant or capacitance under the condition where a dc-bias is applied.

Summary of the Invention

Problems to be Solved by the Invention

[0005] One of the various objects of the present invention is to provide a dielectric and a multilayer ceramic electronic component having excellent withstand voltage characteristics while having a high dielectric constant. [[ID=3,2]]

[0006] One of the various objects of the present invention is to provide a dielectric and a multilayer ceramic electronic component having excellent high-temperature reliability.

[0007] One of the various objects of the present invention is to provide a dielectric and a multilayer ceramic electronic component that are excellent in the density and uniformity of the microstructure of the dielectric and can control the secondary phase.

Means for Solving the Problems

[0008] The dielectric according to one embodiment of the present invention is (Ba 1-X Ca X )(Ti 1-y (Zr, Sn, Hf) y )O3 (where 0 ≦ X ≦ 1, 0 ≦ y ≦ 0.5), a first sub-component containing one or more elements among Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Eu, Tm, La, Lu, and Yb, a second sub-component containing Si and / or Al, and a third sub-component containing Ba and / or Ca, and can satisfy at least two of the following relational expressions 1 to 6.

[0009] The multilayer ceramic electronic component according to another embodiment of the present invention includes a ceramic body including a dielectric layer, a first internal electrode, and a second internal electrode, and a first external electrode and a second external electrode disposed on an outer surface of the ceramic body and connected to the first internal electrode and the second internal electrode, respectively. The dielectric layer is (Ba 1-X Ca X )(Ti 1-y (Zr, Sn, Hf) y )O3 (where 0 ≦ X ≦ 1, 0 ≦ y ≦ 0.5), a first sub-component containing one or more elements among Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Eu, Tm, La, Lu, and Yb, a second sub-component containing Si and / or Al, and a third sub-component containing Ba and / or Ca, and can satisfy at least two of the following relational expressions 1 to 6.

[0010] [Relational Expression 1] 0.162 ≦ M Tb / M Dy ≦ 1.20

[0011] ​ 0.176≦M Gd / M Dy ≤0.60

[0012] [Relationship 3] 0.081≦M Sm / M Dy ≤0.176

[0013] [Relationship Equation 4] 0.081≦M Nb / M Dy ≤0.176

[0014] [Relationship 5] 0.60 ≤ M2 / M1 ≤ 1.36

[0015] [Relationship 6] 0.263 ≤ M3 / M2 ≤ 0.455

[0016] In relational equations 1-4, M Tb M Dy M Gd M Sm , and M Nb M1 represents the number of moles of each component of the first minor component relative to 100 moles of the total B-site elements of the main component. In relational equations 5 and 6, M1 is the total number of moles of the first minor component relative to 100 moles of the main component Ti, M2 is the total number of moles of the second minor component relative to 100 moles of the main component Ti, and M3 is the total number of moles of the third minor component relative to 100 moles of the total B-site elements of the main component. [Effects of the Invention]

[0017] One of the various effects of the present invention is that it is possible to provide dielectrics and multilayer ceramic electronic components that have a high dielectric constant while also having excellent voltage resistance characteristics.

[0018] One of the various effects of the present invention is that it can provide dielectric and multilayer ceramic electronic components with excellent high-temperature withstand voltage.

[0019] One of the various effects of the present invention is that it is possible to provide dielectrics and multilayer ceramic electronic components that have excellent density and uniformity of microstructure of the dielectric, as well as controllable secondary phases.

[0020] However, the diverse and beneficial advantages and effects of the present invention are not limited to those described above and can be more easily understood in the process of describing specific embodiments of the present invention. [Brief explanation of the drawing]

[0021] [Figure 1] This is a schematic perspective view of a multilayer ceramic electronic component according to one embodiment of the present invention. [Figure 2] Figure 1 is a schematic perspective view showing the ceramic body. [Figure 3] This is a cross-sectional view along the line I-I' in Figure 1. [Figure 4] This is an enlarged view of area A in Figure 3. [Figure 5] This figure schematically shows the crystal grains of Figure 4. [Figure 6] This is an SEM image of the main component according to an embodiment of the present invention. [Modes for carrying out the invention]

[0022] Embodiments of the present invention will be described below with reference to specific embodiments and accompanying drawings. It should be understood that this does not intend to limit the technology described herein to specific embodiments, but rather to include various modifications, equivalents, and / or alternatives of the embodiments of the present invention. In relation to the description of the drawings, similar reference numerals are used for similar components.

[0023] In order to clearly explain the present invention, parts unrelated to the explanation are omitted in the drawings, thicknesses are enlarged to clearly represent various layers and regions, and components with the same function within the scope of the same concept are described using the same reference numerals.

[0024] In this specification, expressions such as “having,” “may have,” “include,” or “may include” refer to the existence of the feature in question (e.g., numerical values, functions, operations, or components such as parts) and do not exclude the existence of additional features.

[0025] In this specification, expressions such as “A or B,” “A or / and at least one of B,” or “one or more of A or / and B” may include all possible combinations of the items listed together. For example, “A or B,” “A and at least one of B,” or “A or at least one of B” may mean any of the following: (1) including at least one A, (2) including at least one B, or (3) including both at least one A and at least one B.

[0026] In drawings, the X direction can be defined as the first direction, L direction, or length direction; the Y direction as the second direction, W direction, or width direction; and the Z direction as the third direction, T direction, or thickness direction.

[0027] This invention relates to dielectrics, and the dielectrics according to this invention are applicable to electronic components. Examples of electronic components containing the dielectrics of this invention include, but are not limited to, capacitors, inductors, piezoelectric elements, varistors, or thermistors.

[0028] A dielectric according to one embodiment of the present invention is (Ba 1-X Ca X )(Ti 1-y (Zr, Sn, Hf) y The material comprises a main component represented by O3 (where 0≦X≦1, 0≦y≦0.5), a first minor component containing one or more elements from Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Eu, Tm, La, Lu, and Yb, a second minor component containing Si and / or Al, and a third minor component containing Ba and / or Ca, and can satisfy at least two of the following relations 1 to 6.

[0029] [Relationship 1] 0.162≦M Tb / M Dy ≤1.20

[0030] [Relationship 2] 0.176≦M Gd / M Dy ≤0.60

[0031] [Relationship 3] 0.081≦M Sm / M Dy ≤0.176

[0032] [Relationship Equation 4] 0.081≦M Nb / M Dy ≤0.176

[0033] [Relationship 5] 0.60 ≤ M2 / M1 ≤ 1.16

[0034] [Relationship 6] 0.263 ≤ M3 / M2 ≤ 0.455

[0035] In relational equations 1-4, M Tb M Dy M Gd M Sm , and M Nb M1 represents the number of moles of each component of the first minor component relative to 100 moles of the total B-site elements of the main component. In relational equations 5 and 6, M1 is the total number of moles of the first minor component relative to 100 moles of the main component Ti, M2 is the total number of moles of the second minor component relative to 100 moles of the main component Ti, and M3 is the total number of moles of the third minor component relative to 100 moles of the total B-site elements of the main component.

[0036] Generally, increasing the fraction of grain boundaries in a dielectric, which includes crystal grains and grain boundaries, can reduce charge mobility using the potential barrier at the interface. For this reason, dielectrics with a small grain distribution have been studied to increase the fraction of grain boundaries. However, as the dielectric thickness decreases, the electric field strength increases rapidly, and the phenomenon of a lower Schottky barrier becomes relatively common. Therefore, simply adjusting the grain distribution makes it difficult to ensure the reliability of dielectrics in ultrathin-layer environments.

[0037] Furthermore, within the crystal grains, during the manufacturing process of electronic components, firing in a reducing atmosphere is often performed to prevent oxidation of electrodes and other components. This low oxygen partial pressure leads to the formation of oxygen vacancies and electrons. Therefore, to improve the reliability of the crystal grain interior in ultrathin-layer environments, it is necessary to control both ionic conductivity due to oxygen vacancies and electronic conductivity (electron / hole conductivity).

[0038] The inventors have found that by minimizing oxygen vacancies, which are the main cause of deterioration in the insulation resistance (IR) of electronic components, using the above relational equations 1 to 6, the amount of charge generated itself can be reduced, and the Schottky barrier can be strengthened by ensuring that components with a higher work function than the work function of the principal component are uniformly distributed at the grain boundaries. A dielectric material according to one embodiment of the present invention can minimize the flow of charge moving through the grain boundaries by satisfying two or more of the above relational equations 1 to 6, and can suppress conduction phenomena inside the crystal grains by ensuring that the inside of the crystal grains has a high n-type tendency.

[0039] In one example of the present invention, the dielectric according to the present invention can satisfy at least two of the above-described relations 1 to 4. In this specification, satisfying at least two relations can mean satisfying two of the relations in question, or satisfying three or more relations.

[0040] Of the above relationships, relationships 1 to 4 relate to the amount of charge generated within the crystal grain. Rare earth elements tend to act as donors when substituted at site A and as acceptors when substituted at site B. In this case, the ionic radius is an important factor in determining which site, A or / or B, the substitution occurs at. Therefore, amphoteric elements such as Dy and Tb are selectively substituted at either site A or site B, while other elements with intermediate ionic radii, such as Ho and Y, can play a role in balancing acceptors and donors. Elements with a relatively larger ionic radius than Dy tend to function as donors, and the balance at site A can be adjusted by using elements such as Gd, Sm, and Nb together with Dy and / or Y. On the other hand, excessive use of the above components can lead to a decrease in the reliability of electronic components. Therefore, as with the dielectric material in this example, if at least two of the above relational equations 1 to 4 are satisfied, the generation of oxygen vacancies within the crystal grains can be minimized, and the generation of electric charge can be suppressed.

[0041] In one embodiment of the present invention, the dielectric material according to the present invention can satisfy the above-described relations 5 and 6.

[0042] Of the above relations, relations 5 and 6 relate to charge transfer at grain boundaries. As mentioned above, conventionally, a method has been used to increase the high-resistivity component by reducing the size of the grain boundaries and increasing the fraction of grain boundaries. However, when relations 5 and / or 6 are satisfied, the second subcomponent with a high work function can be uniformly distributed at the grain interface, thereby suppressing the charge release phenomenon. In addition, in order to balance the dielectric constant and bulk resistance, it is necessary to consider both the content of the third subcomponent, which adjusts the sintering temperature, and / or the content of the first subcomponent, which suppresses charge transfer inside the grains. If the values ​​fall outside the range of relations 5 and / or 6, there is a risk of a decrease in dielectric constant and a decrease in reliability.

[0043] In one example, the dielectric material according to the present invention can satisfy one of the above-described relations 1 to 4 and one of relations 5 and 6. In this case, both the suppression of bulk resistance within the crystal grains and the suppression of charge emission at the crystal grain boundaries can be achieved.

[0044] In other examples, the dielectric according to the present invention can satisfy at least two of the above-described relations 1 to 4, and can also satisfy relations 5 and 6. That is, it can satisfy two or more of the relations 1 to 4, and can also satisfy all of relations 5 and 6. In this example, the reliability of the inside of the crystal grains and the crystal grain boundaries can be further improved.

[0045] In one embodiment of the present invention, the dielectric material according to the present invention can satisfy all of the above-described relational equations 1 to 6. In this case, it is possible to maximize the suppression of charge generation and conduction within the crystal grains and the high resistance of the crystal grain boundaries.

[0046] In another embodiment of the present invention, the above-described relational equations 1 to 4 can correspond to the following relational equations 1-1 to 4-1, respectively.

[0047] [Relationship 1-1] 0.108≦(M Tb / MDy ) / M3≦0.800

[0048] [Relationship 2-1] 0.118≦(M Gd / M Dy ) / M3≦0.400

[0049] [Relationship 3-1] 0.054≦(M Sm / M Dy ) / M3≦0.118

[0050] [Relationship 4-1] 0.054≦(M Nb / M Dy ) / M3≦0.118

[0051] In the above relational equations 1-1 to 4-1, M Tb M Dy M Gd M Sm M Nb , and M3 may have the same meaning as described above. That is, M Tb M Dy M Gd M Sm , and M Nb M3 can be the number of moles of each component of the first minor component relative to 100 moles of the total B-site elements of the main component, and M3 can be the total number of moles of the third minor component relative to 100 moles of the total B-site elements of the main component.

[0052] If the dielectric according to this embodiment satisfies one or more of the above-described relations 1 to 4, it can further satisfy the corresponding relations from relations 1-1 to 4-1. The correspondence of relations 1 to 4 to relations 1-1 to 4-1 can mean that relations 1 corresponds to relations 1-1, relations 2 corresponds to relations 2-1, relations 3 corresponds to relations 3-1, and relations 4 corresponds to relations 4-1. In other words, in this embodiment, if the dielectric satisfies relations 1, it can mean that relations 1-1 is also satisfied.

[0053] The above relational equations 1-1 to 4-1 relate to the optimal range of components for suppressing the generation of charge within the crystal grains. The first minor component of the dielectric according to the present invention plays a role in suppressing the generation of oxygen vacancies through a balance of donors and acceptors, thereby reducing conductivity within the crystal grains. In particular, when the above first minor component is substituted at the A site and functions as a donor, it is effective in reducing the concentration of oxygen vacancies. However, if used in amounts exceeding a certain level, excessive semiconductorization may occur due to an increase in electron concentration, potentially leading to a rapid decrease in insulation resistance. Therefore, the above relational equations 1-1 to 4-1 indicate an appropriate range for the content of the first minor component acting on the Ba- site, i.e., the A site. By satisfying the above relational equations 1-1 to 4-1, the bulk resistance within the crystal grains can be increased to the maximum extent.

[0054] A dielectric according to one embodiment of the present invention includes a main component and a minor component, the minor component may include at least one of the first to sixth minor components. In this specification, "main component" means a component that occupies a relatively large weight ratio compared to other components, and may mean a component that accounts for 50% or more by weight based on the total weight of the dielectric. Also, "minor component" means a component that occupies a relatively small weight ratio compared to other components, and may mean a component that accounts for less than 50% by weight based on the total weight of the dielectric.

[0055] The following describes in more detail the components of the dielectric according to one embodiment of the present invention.

[0056] a) Main component (Ba 1-X Ca X )(Ti 1-y (Zr, Sn, Hf) yThe composition formula may include a main component represented by )O3 (where 0≦X≦1, 0≦y≦0.5). The main component may be a chemical compound that exists in a form in which Ca, Zr, Sn, and / or Hf are partially dissolved in BaTiO3. In the composition formula above, X may be in the range of 0 to 1 and y may be in the range of 0 to 0.5, but is not limited to these ranges. For example, in the composition formula above, if X is 0, y is 0 and z is 0, the main component may be BaTiO3.

[0057] b) First subcomponent According to one embodiment of the present invention, the dielectric according to the present invention may contain a first minor component comprising one or more elements from among Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Eu, Tm, La, Lu, and Yb.

[0058] The above-mentioned first minor component may be included in an amount of 0.3 moles or more and / or 5.4 moles or less per 100 moles of the total B-site elements of the main component. The content of the above-mentioned first minor component may be determined based on the content of at least one element from among Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Eu, Tm, La, Lu, and Yb, without distinguishing between the additive form such as oxide or carbonate.

[0059] In one embodiment of the present invention, the above-mentioned first subcomponent plays a role in preventing a decrease in the reliability of the multilayer ceramic electronic component to which the dielectric is applied. If the above-mentioned first subcomponent falls outside the range described above, there is a risk that the high-temperature withstand voltage characteristics will deteriorate.

[0060] c) Second subcomponent According to one embodiment of the present invention, the dielectric material may contain a second minor component comprising Si and / or Al. While the Si element is incorporated in the form of a carbonate, oxide, and / or glass at the raw material stage, it can be included in the dielectric layer in the form of an oxide and / or glass after the sintering process. The Si component is mainly distributed at the grain boundaries and, having a high work function, can enhance the resistance at the grain boundaries. This makes it possible to realize multilayer ceramic electronic components with excellent reliability.

[0061] The above-mentioned second minor component may be included in an amount of 0.5 moles or more and / or 5.0 moles or less per 100 moles of the total B-site elements of the main component. The content of the above-mentioned second minor component may be based on the content of Si elements contained in the second minor component, without distinguishing between the additive form such as glass, oxide, or carbonate.

[0062] If the content of the above-mentioned second minor component is less than 0.5 moles per 100 moles of the total B-site elements of the main component, the dielectric constant and high-temperature internal voltage may decrease. If it is included in amounts exceeding 5.0 moles, the sinterability and density may decrease, and problems such as secondary phase formation may occur.

[0063] d) Third subcomponent According to one embodiment of the present invention, the dielectric according to the present invention may include a third minor component comprising Ba and / or Ca.

[0064] The above-mentioned third minor component may be included in an amount of 0.5 moles or more and / or 3.0 moles or less per 100 moles of the total B-site elements of the main component. The lower limit of the above-mentioned third minor component may be, for example, 0 moles or more or more than 0 moles per 100 moles of the main component. The content of the above-mentioned third minor component may be based on the content of at least one element among Ba and Ca contained in the third minor component, without distinguishing between the additive form such as oxide or carbonate.

[0065] The crystal structure of the dielectric material according to the present invention can be adjusted by including the above-mentioned third minor component in an amount of 5.0 molar parts or less relative to 100 moles of the total B-site elements of the main component.

[0066] e) Fourth subcomponent According to one embodiment of the present invention, the dielectric according to the present invention may contain a fourth minor component including Mg.

[0067] The above-mentioned fourth minor component can function as a fixed-valence acceptor element and may be present in an amount of 0.25 moles or more and / or 1.0 moles or less per 100 moles of the total B-site elements of the main component. The content of the above-mentioned fourth minor component can be determined based on the content of Mg element contained in the fourth minor component, without distinguishing between the additive form such as oxide or carbonate.

[0068] If the content of the fourth minor component exceeds 1.0 molar part per 100 moles of the total B-site elements of the main component, the dielectric constant may decrease, potentially leading to a problem of reduced high-temperature dielectric strength.

[0069] In one example, the ratio M4 / M3 of the content of the fourth subcomponent to the content M3 of the third subcomponent can satisfy the range of 0.125 or more and / or 0.500 or less. By ensuring that the ratio of the third subcomponent to the fourth subcomponent satisfies the above range, abnormal grain growth of the dielectric is suppressed, and the formation of uniform crystal grains is possible.

[0070] f) Fifth subcomponent According to one embodiment of the present invention, the dielectric according to the present invention may contain a fifth minor component comprising one or more of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn.

[0071] The above fifth minor component can function as a variable-valence acceptor element and may be present in an amount of 0.1 moles or more and / or 1.0 moles or less per 100 moles of the total B-site elements of the main component. The content of the above fifth minor component can be determined based on the content of at least one of the elements Mn, V, Cr, Fe, Ni, Co, Cu, and Zn contained in the fifth minor component, without distinguishing between the added form such as oxide or carbonate. For example, if the above fifth minor component contains 0.1 moles of V2O5, which is an oxide of V, the total content of V may be 0.2 moles.

[0072] The fifth minor component described above plays a role in improving the reduction resistance of the dielectric composition and enhancing the high-temperature withstand voltage characteristics of multilayer ceramic electronic components to which the dielectric is applied.

[0073] In one example, the dielectric of the present invention may include a plurality of grains containing the above-mentioned main components and grain boundaries arranged between two or more grains. Figure 4 is a schematic diagram illustrating the microstructure of a dielectric according to one embodiment of the present invention. The dielectric according to the present invention may be formed by sintering the above-mentioned main components and minor components. The dielectric 111 formed by sintering the main components and minor components may include grains 11 and grain boundaries 11c.

[0074] The above crystal grain may include a core portion and a shell portion, and the shell portion may be arranged to surround the core portion. In this case, the average diameter D1 of the core portion may be 5 nm or more and 100 nm or less, and the average diameter D2 of the crystal grain may be 50 nm or more and 600 nm or less. Figure 5 is a schematic diagram of the above crystal grain. Referring to Figure 5, the above crystal grain may have a core portion arranged inside the shell portion. The core portion may mean the region in which the minor components are not solid-dissolved, and the shell portion may mean the remaining region excluding the core portion. The core portion and the shell portion can be distinguished by analyzing the TEM-EDS image of the cross-section.

[0075] The average diameter D1 of the core and the average diameter D2 of the crystal grains can be measured by scanning the central part of the lengthwise and thicknesswise cross-section (LT cross-section) cut in the center of the widthwise direction of the main body using a transmission electron microscope (TEM) at 10,000x magnification. The core and shell can be distinguished from the above image using energy dispersive spectroscopy (EDS). At this time, the core and shell can be distinguished by different colors depending on the presence or absence of solid solution of minor components. After distinguishing the core and shell, any 10 crystal grains having a core-shell structure can be selected from the above image, and the average value of the maximum diameter of each crystal grain can be taken as D2, and the average value of the maximum diameter of the core for each crystal grain can be taken as D1.

[0076] In another embodiment of the present invention, the dielectric according to the present invention is (Ba 1-X Ca X )(Ti 1-y (Zr, Sn, Hf) yThe material contains a main component represented by O3 (where 0≦X≦1, 0≦y≦0.5), and includes a plurality of crystal grains coated on the surface with a second minor component containing Si and / or Al, and grain boundaries arranged between two or more crystal grains, wherein the average diameter D1 of the core portion of the crystal grains is 5 nm or more and 100 nm or less, and the average diameter D2 of the crystal grains is 50 nm or more and 600 nm or less.

[0077] Figure 6 is an SEM image of barium titanate (BaTiO3) particles coated with SiO2 on their surface. Referring to Figure 6, it can be seen that by attaching Si to the surface of the base material during the manufacturing stage of the main component and then heat-treating it, it is possible to uniformly coat the surface of the main component with Si. When forming a dielectric using a main component with a uniform Si coating on its surface, it is possible to coat the surface of the crystal grains with Si, and by ensuring that Si is uniformly distributed in the grain boundary region after sintering, the improvement in resistance at the grain boundaries can be maximized.

[0078] Furthermore, the present invention relates to multilayer ceramic electronic components.

[0079] Figure 1 is a schematic perspective view showing a multilayer ceramic electronic component according to one embodiment of the present invention, Figure 2 is a perspective view showing the ceramic body of Figure 1, Figure 3 is a cross-sectional view along the line I-I' in Figure 1, and Figure 4 is an enlarged view of region A in Figure 3.

[0080] Referring to Figures 1 to 4, a multilayer ceramic electronic component 100 according to one embodiment of the present invention may include a ceramic body 110 comprising a dielectric layer 111, a first internal electrode 121, and a second internal electrode 122. The outer surface of the ceramic body 110 may include a first external electrode 131 connected to the first internal electrode 121 and a second external electrode 132 connected to the second internal electrode 122.

[0081] In this case, the dielectric layer is (Ba 1-X Ca X )(Ti 1-y (Zr, Sn, Hf) yThe material comprises a main component represented by O3 (where 0≦X≦1, 0≦y≦0.5), a first minor component containing one or more elements from Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Eu, Tm, La, Lu, and Yb, a second minor component containing Si and / or Al, and a third minor component containing Ba and / or Ca, and can satisfy at least two of the following relations 1 to 6.

[0082] [Relationship 1] 0.162≦M Tb / M Dy ≤1.20

[0083] [Relationship 2] 0.176≦M Gd / M Dy ≤0.60

[0084] [Relationship 3] 0.081≦M Sm / M Dy ≤0.176

[0085] [Relationship Equation 4] 0.081≦M Nb / M Dy ≤0.176

[0086] [Relationship 5] 0.60 ≤ M2 / M1 ≤ 1.16

[0087] [Relationship 6] 0.263 ≤ M3 / M2 ≤ 0.455

[0088] In relational equations 1-4, M Tb M Dy M Gd M Sm , and M Nb M1 represents the number of moles of each component of the first minor component relative to 100 moles of the total B-site elements of the main component. In relational equations 5 and 6, M1 is the total number of moles of the first minor component relative to 100 moles of the main component Ti, M2 is the total number of moles of the second minor component relative to 100 moles of the main component Ti, and M3 is the total number of moles of the third minor component relative to 100 moles of the total B-site elements of the main component.

[0089] The specific shape of the ceramic body 110 is not particularly limited, but as shown in the figure, the ceramic body 110 may have a hexahedral shape or a similar shape. Due to the shrinkage of the ceramic powder contained in the ceramic body 110 during the firing process, the ceramic body 110 may not have a perfectly straight hexahedral shape, but may have a substantially hexahedral shape.

[0090] The ceramic body 110 described above can be formed by alternately stacking ceramic green sheets, each having a first internal electrode 121 printed on a dielectric layer 111, and ceramic green sheets, each having a second internal electrode 122 printed on a dielectric layer 111, in the thickness direction (Z direction).

[0091] The ceramic body 110 described above can have dielectric layers 111 and internal electrodes 121 and 122 alternately stacked in a third direction. The multiple dielectric layers 111 forming the ceramic body 110 are in a sintered state, and the boundaries between adjacent dielectric layers 111 can be integrated to such an extent that they are difficult to confirm without using a scanning electron microscope (SEM).

[0092] According to one embodiment of the present invention, the dielectric layer 111 is such that the dielectric has a layered structure, (Ba 1-X Ca X )(Ti 1-y (Zr, Sn, Hf) y The material forming the dielectric layer 111 may contain a main component and a minor component represented by O3 (where 0≦X≦1, 0≦y≦0.5). In addition to the main component and minor component of the dielectric described above, the material forming the dielectric layer 111 may also contain various ceramic additives, organic solvents, plasticizers, binders, dispersants, etc., depending on the purpose of the present invention.

[0093] The dielectric layer 111 can be formed by adding an additive, if necessary, to the slurry containing the above-described main component and sub-components, applying the slurry onto a carrier film, and drying it to prepare a plurality of ceramic sheets. The ceramic sheet can be formed by manufacturing the slurry into a sheet having a thickness of several μm by a doctor blade method, but is not limited thereto.

[0094] In another embodiment of the present invention, the above-described relational expressions 1 to 4 can respectively correspond to the following relational expressions 1-1 to 4-1.

[0095] [Relational expression 1-1] 0.162 ≦ (M Tb / M Dy ) / M3 ≦ 1.20

[0096] [Relational expression 2-1] 0.176 ≦ (M Gd / M Dy ) / M3 ≦ 0.60

[0097] [Relational expression 3-1] 0.081 ≦ (M Sm / M Dy ) / M3 ≦ 0.176

[0098] [Relational expression 4-1] 0.081 ≦ (M Nb / M Dy ) / M3 ≦ 0.176

[0099] In one embodiment of the present invention, the multilayer ceramic electronic component according to the present invention further includes a fourth sub-component containing Mg, and the ratio M4 / M3 of the content M4 of the fourth sub-component to the content M3 of the third sub-component can satisfy a range of 0.125 or more and / or 0.500 or less.

[0100] In another embodiment of the present invention, the multilayer ceramic electronic component according to the present invention comprises a plurality of crystal grains containing the above-mentioned main components and crystal grain boundaries arranged between two or more crystal grains, wherein the average diameter D1 of the core portion of the crystal grains is 5 nm or more and 100 nm or less, and the average diameter D2 of the crystal grains is 50 nm or more and 600 nm or less.

[0101] The dielectric layer described above may contain the principal component and the first to fifth minor components. The details regarding the principal component, minor components, relationships, and average diameter are as described above and are therefore omitted here.

[0102] The first and second internal electrodes 121 and 122 can be laminated such that their respective end faces are exposed at opposite ends of the ceramic body 110. The material used to form the first and second internal electrodes 121 and 122 is not particularly limited and can be formed using a conductive paste containing one or more substances from among silver (Ag), palladium (Pd), gold (Au), platinum (Pt), nickel (Ni), copper (Cu), tin (Sn), tungsten (W), titanium (Ti), and alloys thereof. Screen printing or gravure printing can be used as the printing method for the conductive paste, but the present invention is not limited thereto.

[0103] In one example of the present invention, a multilayer ceramic electronic component may have a first external electrode 131 and a second external electrode 132 arranged on the outer surface of the ceramic body. The first external electrode 131 may be connected to a first internal electrode 121, and the second external electrode 132 may be connected to a second internal electrode 122.

[0104] The first external electrode 131 and the second external electrode 132 may include conductive metals. The conductive metal may be one or more conductive metals from among copper (Cu), nickel (Ni), tin (Sn), palladium (Pd), platinum (Pt), gold (Au), silver (Ag), tungsten (W), titanium (Ti), lead (Pb), and alloys thereof, but is not limited thereto.

[0105] The present invention will be described in more detail below with reference to experimental examples, but these are merely for the purpose of providing a concrete understanding of the invention, and the scope of the present invention is not limited by these experimental examples.

[0106] [Example of experiment] As the main component raw material, BaTiO3 powder with an average particle size of 30 nm to 100 nm was used. The main and minor component raw materials corresponding to compositions 1-1 to 5-3 as specified in Table 1 below were mixed with ethanol / toluene and a dispersant using zirconia balls as the mixing / dispersion medium, and mechanical milling was performed for 10 hours. Then, after mixing the above mixture with a binder, milling was performed for another 10 hours.

[0107] Using the manufactured slurry, molded sheets with thicknesses of 0.8 μm and 10 μm were produced using a head-dispensing on-roll coater. Then, Ni internal electrodes were printed onto these molded sheets.

[0108] Multiple layers of the above molded sheets were laminated, and ceramic sheets for margin areas were attached to both sides of the cover sheet and the chip to produce a crimped bar. Green chips of size 0603 (width x length x height: 0.6 mm x 0.3 mm x 0.3 mm) were produced from the crimped bar using a cutting torch.

[0109] The completed 0603 size prototype chips were first calcined at approximately 900°C, then fired in a reducing atmosphere of 0.1% H2 / 99.9% N2 to 1.0% H2 / 99.0% N2 (H2O / H2 / N2 atmosphere) at approximately 1200°C for a duration of 10 minutes to 1 hour, followed by a re-oxidation heat treatment at 950°C in an N2 atmosphere for 3 hours.

[0110] The electrical properties of the manufactured prototype chips were measured to comprehensively confirm density, microstructure uniformity, and secondary phase formation. The content of the samples listed below was measured by inductively coupled plasma (ICP) analysis, which was performed using an inductively coupled plasma atomic emission spectrometer (ICP-OES; Optima 7300DV, PerkinElmer). The presence or absence of each element and the relative ratio of elements were measured using TEM and STEM mapping equipment such as the FEI Tiatan cubed G2 60-300.

[0111] [Table 1]

[0112] In Table 1 above, M RE This is the number of moles of the first minor component excluding Dy, and M Dy is the number of moles of Dy, M1 is the total number of moles of the first minor component, and Coated Si represents the case where SiO2 oxide is ionized and uniformly coated onto the surface of BaTiO3.

[0113] [Table 2]

[0114] Table 2 above shows the characteristics of the prototype chips corresponding to the samples with the numbers specified in Table 1. In Table 2 above, M2 is the total number of moles of the second minor component, and M3 is the total number of moles of the third minor component.

[0115] In Tables 1 and 2 above, the dielectric constant was calculated by measuring the capacitance using an LCR meter under the conditions of 1 kHz and AC 0.5 V / μm, and then using the capacitance, the thickness of the dielectric of the prototype chip, the area of ​​the internal electrodes, and the number of layers. As a result, a dielectric constant of less than 1500 was defined as ×, 1500 or more and less than 2000 as △, 2000 or more and less than 3000 as ○, and 3000 or more as ◎.

[0116] The dielectric strength characteristics were measured by taking 10 samples at a time from the manufactured prototype chips and applying a DC 10V / μm voltage while increasing the applied voltage. The threshold voltage at which dielectric breakdown occurs was defined as follows: × if it was less than 20V, △ if it was between 20V and 30V, ○ if it was between 30V and 40V, and ◎ if it was 40V or higher.

[0117] High-temperature reliability was measured using STEP-IR equipment under the condition of applying DC 10V / μm in a high-temperature environment of 105°C, maintaining it for 30 minutes, and then boosting the voltage. The IR degradation lifetime was then compared. The criteria for determining high-temperature reliability were based on the lifetime time at which IR degradation occurred. A failure time of less than 3 hours for all 10 chips was defined as ×, 3 hours or more but less than 6 hours as △, 6 hours or more but less than 10 hours as ○, and 10 hours or more as ◎.

[0118] Regarding the structural characteristics of the chip, differences in density and average grain size changes for each part were compared on the fracture surface and polished surface of the sintered chip, as observed by SEM. Of these, density and secondary phase frequency were defined as follows: × if the number of pores and secondary phases per unit area observed in a 50K magnification photograph was 100 or more, △ if it was between 70 and less than 100, ○ if it was between 40 and less than 70, and ◎ if it was less than 40.

[0119] Microstructure uniformity was defined as follows: × if the standard deviation (STDEV) of the overall average grain size is 150 or greater, △ if it is between 120 and 150, ○ if it is between 80 and 120 and 120, and ◎ if it is less than 80.

[0120] Referring to samples 1-8, it can be seen that when Tb / Dy is less than 0.162, excellent dielectric constant results are obtained, but structural properties, dielectric strength, and high-temperature reliability deteriorate. Conversely, when Tb / Dy exceeds 1.20, structural properties are excellent, but electrical properties such as dielectric strength and high-temperature reliability deteriorate. Therefore, it can be confirmed that the Tb / Dy content ratio must be within the range of 0.162 or higher and / or 1.20 or lower.

[0121] Referring to samples 9-15, it can be seen that when the Gd / Dy ratio is less than 0.176, excellent structural properties and dielectric constant are obtained, but dielectric strength and high-temperature reliability decrease. Similarly, when the Gd / Dy ratio exceeds 0.60, electrical properties such as dielectric strength and high-temperature reliability also decrease. Therefore, it can be confirmed that the Gd / Dy content ratio must be within the range of 0.176 or higher and / or 0.60 or lower.

[0122] Referring to samples 16-22, it can be seen that when the Sm / Dy ratio is less than 0.081, very poor results are obtained in terms of dielectric strength and high-temperature reliability. Conversely, when the Sm / Dy ratio exceeds 0.176, excellent dielectric constant is observed, but electrical properties such as dielectric strength and high-temperature reliability deteriorate. Therefore, it can be confirmed that the Sm / Dy content ratio must be within the range of 0.081 or higher and / or 0.176 or lower.

[0123] Referring to samples 23-29, it can be seen that when the Nb / Dy ratio is less than 0.081, very poor results are obtained in terms of dielectric strength and high-temperature reliability. Conversely, when the Nb / Dy ratio exceeds 0.176, excellent dielectric constant is observed, but electrical properties such as dielectric strength and high-temperature reliability deteriorate. Therefore, it can be confirmed that the Nb / Dy content ratio must be within the range of 0.081 or higher and / or 0.176 or lower.

[0124] Referring to samples 30-49, it can be confirmed that even when the same content of the first minor component is applied, if the content of the second minor component is added in a ratio outside the appropriate range, the dielectric constant and density decrease. Similarly, even when the same content of Si is applied, if the ratio of its content to that of the third minor component falls outside the specified range, the dielectric constant decreases. Therefore, it can be confirmed that even if the content of the first minor component, which corresponds to a rare earth element, is the same, the ratio of its content to that of the second and third minor components has a significant impact.

[0125] Samples 50-54 show results using a main component coated with Si on its surface. Referring to samples 50-54, it can be confirmed that when Si is uniformly distributed on the surface of the main component, better electrical properties can be obtained even if the content of the first minor component is the same. In other words, it can be confirmed that by adjusting the distribution of Si on the surface of the main component to be uniform, the interfacial resistance at the grain boundary can be improved more effectively.

[0126] Although embodiments of the present invention have been described in detail above, the present invention is not limited by the embodiments described above and the accompanying drawings, but is intended to be limited by the attached claims. Therefore, within the scope of the technical idea of ​​the present invention as described in the claims, various forms of substitution, modification, and alteration are possible by persons with ordinary skill in the art, and these also fall within the scope of the present invention. [Explanation of Symbols]

[0127] 100 Multilayer Ceramic Electronic Components 110 Ceramic body 111 Dielectric layer 121, 122 First internal electrode and second internal electrode 131, 132 First external electrode and second external electrode 11 crystal grains 11a core 11b Shell 11c grain boundaries

Claims

1. (Ba １－Ｘ Ca Ｘ ) (Ti １－ｙ (Zr, Sn, Hf) ｙ ) O ３ A dielectric comprising a main component represented by (where 0 ≤ X ≤ 1, 0 ≤ y ≤ 0.5), a first minor component containing one or more elements from Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Nb, Tb, Eu, Tm, La, Lu, and Yb, a second minor component containing Si and / or Al, and a third minor component containing Ba and / or Ca, satisfying at least two of the following relations 1 to 4. [Relationship 1] 0.162≦M Ｔｂ / M Ｄｙ ≦1.20 [Relationship Equation 2] 0.176≦M Ｇｄ / M Ｄｙ ≦0.60 [Relationship Equation 3] 0.081≦M Ｓｍ / M Ｄｙ ≦0.176 [Relational Equation 4] 0.081≦M Ｎｂ / M Ｄｙ ≦0.176 [Relationship Equation 5] 0.60≦M ２ / M １ ≦1.16 [Relational Equation 6] 0.263≦M ３ / M ２ ≦0.455 (In relational equations 1 to 4, M Ｔｂ M Ｄｙ M Ｇｄ M Ｓｍ , and M Ｎｂ This represents the number of moles of each component of the first minor component relative to the total of 100 moles of the B-site element of the main component, and in relational equations 5 and 6, M １ This is the total number of moles of the first minor component relative to 100 moles of the main component Ti, and M ２ This is the total number of moles of the second minor component relative to 100 moles of the main component Ti, and M ３ (This is the total number of moles of the third minor component relative to 100 moles of the B-site element, which is the main component.)

2. The dielectric according to claim 1, further satisfying one of the relational expressions 5 and 6.

3. The dielectric according to claim 1, further satisfying the relational equations 5 and 6.

4. The dielectric according to claim 1, satisfying the aforementioned relational equations 1 to 6.

5. The aforementioned relational equations 1 to 4 correspond to the following relational equations 1-1 to 4-1, The dielectric according to any one of claims 1 to 4, wherein if any one or more of the above relational expressions 1 to 4 is satisfied, the corresponding relational expression from the following relational expressions 1-1 to 4-1 is further satisfied. [Relationship 1-1] 0.108≦(M Ｔｂ / M Ｄｙ ) / M ３ ≦0.800 [Relationship 2-1] 0.118≦(M Ｇｄ / M Ｄｙ ) / M ３ ≦0.400 [Relationship 3-1] 0.054≦(M Ｓｍ / M Ｄｙ ) / M ３ ≦0.118 [Relational Equation 4-1] 0.054≦(M Ｎｂ / M Ｄｙ ) / M ３ ≦0.118

6. The dielectric according to any one of claims 1 to 5, wherein the content of the third minor component is in the range of 0.5 moles or more and / or 3.0 moles or less with respect to 100 moles of the total B-site elements of the main component.

7. It further contains a fourth minor component containing Mg, The dielectric according to any one of claims 1 to 6, wherein the content of the fourth minor component is in the range of 0.25 moles or more and / or 1.0 moles or less with respect to 100 moles of the total B-site elements of the main component.

8. Content M of the third minor component mentioned above ３ Content M of the fourth minor component relative to ４ Ratio M ４ / M ３ The dielectric according to claim 7, wherein the range is 0.125 or more and / or 0.500 or less.

9. The content of the first minor component satisfies the range of 0.3 moles or more and / or 5.7 moles or less with respect to 100 moles of the total B-site element of the main component. The dielectric according to any one of claims 1 to 8, wherein the content of the second minor component is in the range of 0.5 moles or more and / or 6.5 moles or less with respect to 100 moles of the total B-site elements of the main component.

10. It contains a fifth minor component which includes one or more of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn. The dielectric according to any one of claims 1 to 9, wherein the content of the fifth minor component is in the range of 0.1 moles or more and / or 1.0 moles or less per 100 moles of total B-site elements.

11. The system comprises a plurality of crystal grains containing the aforementioned main component, and a grain boundary disposed between two or more crystal grains. The average diameter D1 of the core portion of the crystal grains is between 5 nm and 100 nm. The dielectric according to any one of claims 1 to 10, wherein the average diameter D2 of the crystal grains is 50 nm or more and 600 nm or less.

12. The plurality of crystal grains are coated on the surface with the second minor component. The dielectric according to claim 11.

13. A ceramic body including a dielectric layer, a first internal electrode, and a second internal electrode, The ceramic body includes a first external electrode and a second external electrode, which are arranged on the outer surface of the ceramic body and connected to the first internal electrode and the second internal electrode, respectively. The dielectric layer is (Ba １－Ｘ Ca Ｘ ) (Ti １－ｙ (Zr, Sn, Hf) ｙ ) O ３ A multilayer ceramic electronic component comprising a main component represented by (where 0 ≤ X ≤ 1, 0 ≤ y ≤ 0.5), a first minor component containing one or more elements from among Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Nb, Tb, Eu, Tm, La, Lu, and Yb, a second minor component containing Si and / or Al, and a third minor component containing Ba and / or Ca, satisfying at least two of the following relational expressions 1 to 4. [Relationship 1] 0.162≦M Ｔｂ / M Ｄｙ ≦1.20 [Relationship Equation 2] 0.176≦M Ｇｄ / M Ｄｙ ≦0.60 [Relationship Equation 3] 0.081≦M Ｓｍ / M Ｄｙ ≦0.176 [Relational Equation 4] 0.081≦M Ｎｂ / M Ｄｙ ≦0.176 [Relationship Equation 5] 0.60≦M ２ / M １ ≦1.36 [Relational Equation 6] 0.263≦M ３ / M ２ ≦0.455 (In relational equations 1 to 4, M Ｔｂ M Ｄｙ M Ｇｄ M Ｓｍ , and M Ｎｂ This represents the number of moles of each component of the first minor component relative to the total of 100 moles of the B-site element of the main component, and in relational equations 5 and 6, M １ This is the total number of moles of the first minor component relative to 100 moles of the main component Ti, and M ２ This is the total number of moles of the second minor component relative to 100 moles of the main component Ti, and M ３ (This is the total number of moles of the third minor component relative to 100 moles of the B-site element, which is the main component.)

14. The aforementioned relational equations 1 to 4 correspond to the following relational equations 1-1 to 4-1, The multilayer ceramic electronic component according to claim 13, wherein if any one or more of the above relational expressions 1 to 4 is satisfied, the corresponding relational expression from the following relational expressions 1-1 to 4-1 is further satisfied. [Relationship 1-1] 0.108≦(M Ｔｂ / M Ｄｙ ) / M ３ ≦0.800 [Relationship 2-1] 0.118≦(M Ｇｄ / M Ｄｙ ) / M ３ ≦0.400 [Relationship 3-1] 0.054≦(M Ｓｍ / M Ｄｙ ) / M ３ ≦0.118 [Relational Equation 4-1] 0.054≦(M Ｎｂ / M Ｄｙ ) / M ３ ≦0.118

15. It further contains a fourth minor component containing Mg, Content M of the third minor component mentioned above ３ Content M of the fourth minor component relative to ４ Ratio M ４ / M ３ The multilayer ceramic electronic component according to claim 13 or 14, wherein the range is 0.125 or more and / or 0.500 or less.

16. The system comprises a plurality of crystal grains containing the aforementioned main component, and a grain boundary disposed between two or more crystal grains. The average diameter D1 of the core portion of the crystal grains is between 5 nm and 100 nm. The multilayer ceramic electronic component according to any one of claims 13 to 15, wherein the average diameter D2 of the crystal grains is 50 nm or more and 600 nm or less.

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