KR102516760B1 - Dielectric composition and multilayer ceramic capacitor comprising the same - Google Patents

Abstract

According to an embodiment of the present invention, a (Ba,Ti)O ₃ based ferroelectric material is used as a first main component and a (Ca,Sr)(Zr,Ti)O ₃ based paraelectric material is used as a second main component, When the mole fraction of the first main component is a and the mole fraction of the second main component is b, the condition of 0.33≤a/b≤3 is satisfied, and the second main component has the composition formula (Ca,Sr) ( It is represented by Zr _{1 - x} Ti _x )O ₃ , where x satisfies the condition of 0.2≤x≤0.8, and a multilayer ceramic capacitor including the same may be implemented.

Description

Dielectric composition and multilayer ceramic capacitor including the same

The present invention relates to a novel dielectric composition capable of satisfying X5R, X7R, and X8R temperature characteristics and improving reliability, and a multilayer ceramic capacitor including the same.

Recently, heat generation in electronic devices has become serious due to the increase in the size of video devices and the increase in CPU speed of computers, so the X5R ( -55℃~85℃ operating temperature) or X7R (-25℃~125℃ operating temperature), and further, the market demand for X8R (-55℃~150℃) class models is growing.

In addition, miniaturization, high capacity, and boosting of multilayer ceramic capacitor (MLCC) chip products are continuously required in order to meet the trend of the general electronic product market, which is miniaturization and multifunctionality. Therefore, in addition to the thinning of the dielectric layer, excellent withstand voltage and DC characteristics are considered important in the development of X5R, X7R, or X8R class models.

Thinning and boosting increase the strength of the electric field applied to the dielectric layer, deteriorating the DC characteristics and withstand voltage characteristics. In particular, defects in the microstructure due to thinning have a more serious effect on withstand voltage characteristics such as BDV (Breakdown Voltage) and high-temperature IR.

One of the objects of the present invention is to provide a novel dielectric composition capable of improving X5R, X7R and X8R temperature characteristics and reliability, and a multilayer ceramic capacitor including the same.

In order to solve the above object, the present invention is intended to provide a dielectric composition containing a ferroelectric and a paraelectric in a unique composition formula and ratio in one embodiment, and specifically, to provide a (Ba,Ti)O ₃ -based ferroelectric material As the first main component, a paraelectric material of the (Ca,Sr)(Zr,Ti)O ₃ series is used as the second main component, the mole fraction of the first main component is a, and the mole fraction of the second main component is b. , the condition of 0.33≤a/b≤3 is satisfied, and the second main component is represented by the composition formula (Ca,Sr)(Zr _{1 - x} Ti _x )O ₃ , where x is 0.2≤x≤0.8 satisfies the condition of

Furthermore, by implementing a multilayer ceramic capacitor using such a dielectric composition, dielectric characteristics, withstand voltage characteristics, and the like can be improved.

According to one embodiment of the present invention, a dielectric composition having a high dielectric constant and excellent withstand voltage characteristics and a multilayer ceramic capacitor including the dielectric composition may be implemented.

FIG. 1 schematically shows the crystal structure of a ferroelectric material and a paraelectric material and an oxygen bond state with a coordinator.
2 is a graph showing a comparison of the behavior of dielectric properties according to temperature in a ferroelectric material and a paraelectric material.
3 is a schematic perspective view illustrating a multilayer ceramic capacitor according to an embodiment of the present invention.
FIG. 4 is a schematic cross-sectional view of the multilayer ceramic capacitor taken along line II′ of FIG. 3 .

Hereinafter, embodiments of the present invention will be described with reference to specific embodiments and accompanying drawings. However, the embodiments of the present invention can be modified in many different forms, and the scope of the present invention is not limited to the embodiments described below. In addition, the embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art. Therefore, the shape and size of elements in the drawings may be exaggerated for clearer explanation, and elements indicated by the same reference numerals in the drawings are the same elements.

In addition, in order to clearly describe the present invention in the drawings, parts irrelevant to the description are omitted, and the thickness is enlarged in order to clearly express various layers and regions, and components having the same function within the scope of the same idea are shown with the same reference. Explain using symbols. Furthermore, throughout the specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

The present invention relates to a dielectric composition, and an electronic component including the dielectric composition includes a capacitor, an inductor, a piezoelectric element, a varistor, or a thermistor. Hereinafter, a multilayer ceramic capacitor will be described as an example of the dielectric composition and the electronic component.

dielectric composition

In a dielectric composition according to an embodiment of the present invention, a (Ba,Ti)O ₃ based ferroelectric material is used as a first main component and a (Ca,Sr)(Zr,Ti)O ₃ based paraelectric material is used as a second main component. And, when the mole fraction of the first main component is a and the mole fraction of the second main component is b, the condition of 0.33≤a/b≤3 is satisfied, and the second main component is given by the composition formula (Ca,Sr )(Zr _{1 -x} Ti _x )O ₃ , where x satisfies the condition of 0.2≤x≤0.8.

A dielectric composition that satisfies these conditions will satisfy the X5R (-55℃ to 85℃), X7R (-55℃ to 125℃), and X8R (-55℃ to 150℃) characteristics specified in EIA (Electronic Industries Association) standards. can

More specifically, according to an embodiment of the present invention, a dielectric composition using nickel (Ni) as an internal electrode and capable of being fired in a reducing atmosphere in which the nickel (Ni) is not oxidized at 1300° C. or less is provided. In addition, by providing a multilayer ceramic capacitor using the same, it is possible to realize excellent reliability while satisfying the temperature characteristics.

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

a) main component

In the case of a dielectric composition according to an embodiment of the present invention, a (Ba,Ti)O ₃ -based ferroelectric material is used as a first main component, and a (Ca,Sr)(Zr,Ti)O ₃ -based paraelectric material is used as a second main component. When the mole fraction of the first main component is a and the mole fraction of the second main component is b, the condition of 0.33≤a/b≤3 is satisfied, and the second main component has a composition formula (Ca ,Sr)(Zr _{1 - x} Ti _x )O ₃ , where x satisfies the condition of 0.2≤x≤0.8.

In this case, the first main component is BaTiO ₃ , (Ba,Ca)(Ti,Ca)O ₃ , (Ba,Ca)(Ti,Zr)O ₃ , Ba(Ti,Zr)O ₃ and (Ba,Ca ) (Ti, Sn) O ₃ It may be represented by at least one composition formula.

According to the reduction model, which is one of the representative degradation models of MLCC, it is known that oxygen voids having high mobility are generated in the basic structure of BaTiO ₃ , and degradation occurs by the movement of these oxygen vacancies. That is, when an electric field is applied in a state in which oxygen vacancies are generated, the oxygen vacancies move toward the cathode and an oxygen vacancy concentration gradient is formed at the cathode, and the anode is reduced while releasing oxygen, thereby increasing the electron concentration.

As such, since the leakage current can be increased by the movement of oxygen vacancies, the inventors of the present invention tried to derive an effective method for controlling the concentration of oxygen vacancies and lowering the mobility. Conventionally, a method of adjusting the addition amount of an acceptor dopant has been used to lower the concentration of electrons or to suppress the movement of electrons, but this has problems such as the occurrence of defects because the stoichiometric ratio is not satisfied.

The generation and movement patterns of such oxygen vacancies differ depending on the material, and the inventors of the present invention paid attention to the difference between a ferroelectric and a paraelectric. 1 schematically shows crystal structures and oxygen bonding states of coordination atoms in ferroelectric materials and paraelectric materials. In FIG. 1, A, B, and O represent each element in the ABO ₃ crystal structure. In addition, FIG. 2 is a graph showing a comparison of the behavior of dielectric properties according to temperature in a ferroelectric material and a paraelectric material.

Referring to FIG. 1, first of all, in the case of a ferroelectric material such as BaTiO ₃ , Ti cations (corresponding to B) located at the body center and oxygen anions coordinating around them are caused by phase transition according to temperature and lattice displacement below the Tc temperature. (corresponding to O) polarization is formed. In the case of ferroelectric materials, because of the unstable bonding between Ti-O atoms, the bonding structure of Ti-O can be more easily destroyed depending on the direction of the applied voltage, and oxygen vacancies are created and mobility increases accordingly. will do

In comparison, a paraelectric material has a constant lattice structure regardless of applied voltage or temperature, and as shown in FIG. 1, oxygen and neighboring atoms coordinating it always maintain a constant distance. Due to this stable structure, it is relatively difficult to generate and move oxygen vacancies in a paraelectric material because it has a high binding energy.

In addition, looking at the dielectric properties of the ferroelectric and paraelectric shown in FIG. 2 below, in the case of ferroelectric, it can be confirmed that the change in permittivity is large due to lattice displacement with temperature. In contrast, paraelectric materials having a stable crystal structure It shows a constant level of permittivity behavior.

Considering the difference in physical properties between heterogeneous materials, the inventors of the present invention tried to suppress degradation of insulating properties due to oxygen vacancies and implement stable temperature characteristics by using a dielectric composition including both ferroelectric and paraelectric materials. Furthermore, as will be described later, the content and composition of each dielectric material were adjusted to an appropriate ratio in consideration of other electrical characteristics, such as electrical resistance, high-temperature withstand voltage characteristics, and temperature characteristics.

Although paraelectric materials have stable characteristics as described above, since dielectric constants are generally lower than those of ferroelectric materials, the amount included in the entire dielectric composition needs to be adjusted in consideration of various characteristics. In addition, according to the research of the present inventors, in the case of (Ca,Sr)(Zr,Ti)O ₃ -based paraelectric materials, the ratio of B-site elements (Zr/Ti) is higher than the ratio of A-site elements (Ca/Sr). It was found that it has a more important effect on dielectric properties and temperature characteristics.

As a result of comprehensively considering the above matters, in the dielectric composition of the present embodiment, the ratio of the first and second main components satisfies the condition of 0.33≤a/b≤3, and the composition formula of the second main component (Ca,Sr)(Zr ₁ In _{- x} Ti _x ) O ₃ , x was set to satisfy the condition of 0.2≤x≤0.8. This will be explained in detail through the experimental results to be described later.

By using the above dielectric composition proposed in the present embodiment, X5R, X7R, and X8R characteristics are satisfied, and further, dielectric characteristics and high-temperature withstand voltage characteristics can be improved.

b) first subcomponent

According to one embodiment of the present invention, the dielectric composition may further include an oxide or carbonate containing at least one of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn as a first subcomponent. The first subcomponent is a variable valence acceptor, and may serve to improve firing temperature reduction and high-temperature withstand voltage characteristics of the multilayer ceramic capacitor to which the dielectric composition is applied. In this case, although not necessarily limited thereto, the first subcomponent may be included in an amount of 0.1 to 1.0 mol% based on 100 mol% of the first and second main components. The content of the first subcomponent and the contents of other subcomponents described later are amounts relative to 100 mol% of the first and second main components, and may be defined as mol% of metal ions included in each subcomponent. When the amount of the first subcomponent is less than 0.1 mol% compared to the first and second main components, reduction resistance and reliability may be deteriorated, and when it is greater than 1.0 mol%, an increase in firing temperature and a decrease in capacity may occur.

c) second subcomponent

According to one embodiment of the present invention, the dielectric composition may further include an oxide or carbonate of at least one of Mg and Al as a second subcomponent. The second subcomponent is a fixed valence acceptor, and may serve to improve firing temperature reduction and high-temperature withstand voltage characteristics of the multilayer ceramic capacitor to which the dielectric composition is applied. In this case, although not necessarily limited thereto, the second subcomponent may be included in an amount of 0.1 to 1.0 mol% based on 100 mol% of the first and second main components. When the second subcomponent is less than 0.1 mol% compared to the first and second main components, reduction resistance and reliability may be deteriorated, and when it is greater than 1.0 mol%, an increase in firing temperature and a decrease in capacity may occur.

c) third subcomponent

According to one embodiment of the present invention, the dielectric composition may further include at least one oxide or carbonate of Ce, Nb, La, and Sb as a third subcomponent. In this case, although not necessarily limited thereto, the third subcomponent may be included in an amount of 0.1 to 1.0 mol% based on 100 mol% of the first and second main components.

c) the fourth subcomponent

According to one embodiment of the present invention, the dielectric composition may further include an oxide or carbonate of at least one of Si, Ba, Ca, and Al as a fourth subcomponent. In this case, although not necessarily limited thereto, the fourth subcomponent may be included in an amount of 0.1 to 1.0 mol% based on 100 mol% of the first and second main components.

Also, as another example of the fourth subcomponent, the dielectric composition may include a glass compound containing Si, and similarly, it may be included in an amount of 0.1 to 1.0 mol% relative to 100 mol% of the first and second main components.

multilayer ceramic capacitors

FIG. 2 is a schematic perspective view of a multilayer ceramic capacitor according to an exemplary embodiment, and FIG. 3 is a schematic cross-sectional view of the multilayer ceramic capacitor taken along line II′ of FIG. 2 .

2 and 3 , a multilayer ceramic capacitor according to another embodiment of the present invention has a ceramic body 110 in which dielectric layers 111 and first and second internal electrodes 121 and 122 are alternately stacked. . At both ends of the ceramic body 110, first and second external electrodes 131 and 132 that are respectively conductive to the first and second internal electrodes 121 and 122 alternately disposed inside the ceramic body 110 are provided. is formed

Although the shape of the ceramic body 110 is not particularly limited, it may generally have a hexahedral shape. In addition, the size is not particularly limited, and it can be set to an appropriate size depending on the application, for example, (0.6 to 5.6 mm) x (0.3 to 5.0 mm) x (0.3 to 1.9 mm).

The thickness of the dielectric layer 111 can be arbitrarily changed according to the capacitance design of the capacitor. In one embodiment of the present invention, the thickness of the dielectric layer after firing may be preferably 0.2 μm or more per layer. The thickness of the dielectric layer may be 0.2 μm or more because a too thin dielectric layer has a small number of crystal grains present in the layer and adversely affects reliability.

The first and second internal electrodes 121 and 122 are stacked so that their cross sections are alternately exposed to surfaces of opposite ends of the ceramic body 110 . The first and second external electrodes 131 and 132 are formed on both ends of the ceramic body 110 and are electrically connected to exposed end surfaces of the alternately disposed first and second internal electrodes 121 and 122 to form a capacitor. make up a circuit

The conductive material included in the first and second internal electrodes 121 and 122 is not particularly limited, but when the ceramic body 110 is formed using the dielectric composition according to an embodiment of the present invention, the temperature is about 1300° C. or less. In addition to firing in a reducing atmosphere, the internal electrodes 121 and 122 may be formed of a material containing a Ni component.

The thickness of the first and second internal electrodes 121 and 122 may be appropriately determined depending on the purpose, and is not particularly limited, but may be, for example, 0.1 to 5 μm or 0.1 to 2.5 μm.

The conductive material included in the first and second external electrodes 131 and 132 is not particularly limited, but nickel (Ni), copper (Cu), or an alloy thereof may be used. The thickness of the first and second external electrodes 131 and 132 may be appropriately determined depending on the purpose, etc., and is not particularly limited, but may be, for example, 10 to 50 μm.

The dielectric layer 111 constituting the ceramic body 110 may include the dielectric composition having the above-described composition according to an embodiment of the present invention.

A detailed description of the dielectric composition is the same as the characteristics of the dielectric composition according to an embodiment of the present invention described above, so it will be omitted here.

Experiment example

Hereinafter, the present invention will be described in more detail through experimental examples performed by the inventors of the present invention, but this is to help a detailed understanding of the present invention, and the scope of the present invention is not limited only by the experimental examples.

The first main component of the base material was 300 nm class BaTiO ₃ powder, and the second main component was 300 nm class (Ca,Sr)(Zr _{1 - x} Ti _x )O ₃ composition formula (indicated by 'CSZT' in Table 1 below) ) was used. And, as shown in Table 1 below, composition samples were prepared while adjusting the ratio of the first and second main components and the ratio of Zr and Ti in the second main component.

Example Base material main component wt% Number of moles of subcomponents per 1 mole of parent material BaTiO ₃ CSZT During CSZT
Zr/Ti ratio Dy ₂ O ₃ BaCO ₃ Mn ₃ O ₄ V ₂ O ₅ Al ₂ O ₃ SiO ₂ Zr Ti One 100 0 0 0 1.00 0.70 0.20 0.05 0.10 1.25 2 75 25 0.8 0.2 3 0.6 0.4 4 0.4 0.6 5 0.2 0.8 6 50 50 0.8 0.2 7 0.6 0.4 8 0.4 0.6 9 0.2 0.8 10 25 75 0.8 0.2 11 0.6 0.4 12 0.4 0.6 13 0.2 0.8 14 0 100 0.8 0.2 15 0.6 0.4 16 0.4 0.6 17 0.2 0.8

To explain the sample manufacturing process in more detail, when preparing the slurry, the base material main component and subcomponent powder were mixed/dispersed using a zirconia ball, and mechanical milling was performed after mixing ethanol/toluene and a °C dispersant. Then, a binder mixing process was added so that the dielectric layer had an appropriate level of strength. The prepared slurry was prepared into a molded sheet with a thickness of 10 to 15 μm using a small doctor blade type molding coater for the production of K2 bulk specimens, and after compression, the thickness of the green specimen was about 0.8 mm. After stacking as much as possible, it was cut into K2 bulk specimens of 1.0cm (width) x 1.0cm (length) size.

The manufactured K2 bulk specimen was calcined at 400 ° C and air, and then fired at a firing temperature of 1300 ° C or less and a hydrogen concentration of 0.5% H ₂ or less. measured. Room temperature capacitance and dielectric loss of MLCC implemented as bulk type K2 were measured at 1kHz and AC 1V using an LCR meter, and 10 samples were taken and room temperature insulation resistance was measured after 60 seconds with DC voltage applied. . The capacity change rate (TCC) according to temperature was performed under the condition of applying a voltage of 1 kHz and AC 1 V in the temperature range of -55 to 125 ° C. The results of the permittivity, resistivity and high-temperature withstand voltage tests for the samples prepared as shown in Table 1 are shown in Table 2 below. Here, the evaluation results are shown together with each characteristic value, ◎ is excellent, ○ is good, Δ is average, and X is poor.

Example characteristic Attribute roll permittivity resistivity
(Ω*cm) High temperature
withstand voltage
(V/μm) TCC
(ΔC@125℃) permittivity resistivity High temperature
withstand voltage TCC One 2400 1.68E+10 58 -15.6% ◎ X X X 2 1859 6.63E+11 132 -10.3% △ O O △ 3 1964 4.05E+11 125 -11.2% △ O O △ 4 2012 2.12E+11 110 -12.4% O △ O △ 5 2123 9.04E+10 92 -13.1% O △ △ △ 6 1532 2.01E+12 156 -5.8% △ O ◎ O 7 1654 1.38E+12 148 -6.2% △ O O O 8 1754 9.98E+11 133 -7.4% △ O O O 9 1852 6.12E+11 129 -8.6% △ O O O 10 1025 2.64E+13 216 -0.7% X ◎ ◎ ◎ 11 1254 1.38E+13 198 -1.6% X ◎ ◎ ◎ 12 1358 8.92E+12 169 -2.1% X O ◎ ◎ 13 1465 6.08E+12 159 -3.8% △ O ◎ ◎ 14 30 9.86E+13 350 -0.005% X ◎ ◎ ◎ 15 75 6.95E+13 278 -0.15% X ◎ ◎ ◎ 16 130 5.90E+13 240 -1.0% X ◎ ◎ ◎ 17 200 8.12E+13 198 -1.6% X ◎ ◎ ◎

Looking at the experimental results of Tables 1 and 2, first of all, as the content of the second main component, which is a paraelectric material, increased, it was observed that the dielectric constant of the entire composition decreased, and on the contrary, resistance, withstand voltage and temperature characteristics tended to be greatly improved. is showing Considering the optimal mixing ratio of the different substances based on the above experimental example, when the mole fraction of the first main component is a and the mole fraction of the second main component is b, the condition of 0.33≤a/b≤3 can be derived.

In addition, looking at the characteristic change according to the ratio of Zr and Ti, it was confirmed that the dielectric constant of the composition containing Ti, a solid solution element at the B site, was relatively high. Specifically, when the Zr/Ti ratio is lowered in the second main component (CSZT), that is, when the content of Ti is relatively increased, in a mixed system of a ferroelectric and a paraelectric, the dielectric that can occur by increasing the ratio of the paraelectric, that is, the second main component The deterioration of properties can be mitigated. Specifically, as the content of the paraelectric material having a relatively low dielectric constant value increases, there is a negative effect of lowering the dielectric constant of the entire composition, but this can be minimized by increasing the content of Ti. As described above, while minimizing the decrease in dielectric constant, it is possible to improve withstand voltage and temperature characteristics through the stable characteristics of the paraelectric material as described above. Considering the optimal mixing ratio of Zr and Ti in the second main component based on the above experiment, the second main component is represented by the composition formula (Ca,Sr)(Zr _{1 - x} Ti _x )O ₃ , where x is 0.2≤x≤ The condition of 0.8 can be derived.

The present invention is not limited by the above-described embodiments and accompanying drawings, but is intended to be limited by the appended claims. Therefore, various forms of substitution, modification, and change will be possible by those skilled in the art within the scope of the technical spirit of the present invention described in the claims, which also falls within the scope of the present invention. something to do.

110: ceramic body
111: dielectric layer
121, 122: first and second internal electrodes
131, 132: first and second external electrodes

Claims (14)

(Ba,Ti)O ₃ series ferroelectric material as a first main component,
(Ca,Sr)(Zr,Ti)O ₃ series paraelectric material as a second main component,
When the mole fraction of the first main component is a and the mole fraction of the second main component is b, the condition of 0.33≤a/b≤3 is satisfied;
The second main component is represented by the composition formula (Ca,Sr)(Zr _{1 - x} Ti _x )O ₃ ,
Here, x is a dielectric composition that satisfies the condition of 0.2≤x≤0.8.
According to claim 1,
The first main component is BaTiO ₃ , (Ba,Ca)(Ti,Ca)O ₃ , (Ba,Ca)(Ti,Zr)O ₃ , Ba(Ti,Zr)O ₃ and (Ba,Ca)(Ti , Sn) O ₃ A dielectric composition represented by at least one compositional formula.
According to claim 1,
A dielectric composition further comprising 0.1 to 1.0 mol% of a first subcomponent that is an oxide or carbonate of at least one of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn relative to 100 mol% of the first and second main components.
According to claim 3,
A dielectric composition further comprising 0.1 to 1.0 mol% of a second subcomponent that is an oxide or carbonate of at least one of Mg and Al relative to 100 mol% of the first and second main components.
According to claim 4,
A dielectric composition further comprising 0.1 to 1.0 mol% of a third subcomponent, which is an oxide or carbonate of at least one of Ce, Nb, La, and Sb, based on 100 mol% of the first and second main components.
According to claim 5,
A dielectric composition further comprising 0.1 to 1.0 mol% of a fourth subcomponent that is an oxide or carbonate of at least one of Si, Ba, Ca, and Al relative to 100 mol% of the first and second main components.
According to claim 5,
A dielectric composition further comprising 0.1 to 1.0 mol% of a fourth subcomponent, which is a glass compound including Si, relative to 100 mol% of the first and second main components.
It includes a ceramic body in which dielectric layers and internal electrodes are alternately laminated,
The dielectric layer,
(Ba,Ti)O ₃ series ferroelectric material as a first main component,
(Ca,Sr)(Zr,Ti)O ₃ series paraelectric material as a second main component,
When the mole fraction of the first main component is a and the mole fraction of the second main component is b, the condition of 0.33≤a/b≤3 is satisfied;
The second main component is represented by the composition formula (Ca,Sr)(Zr _{1 - x} Ti _x )O ₃ ,
Here, x is a multilayer ceramic capacitor including a dielectric composition that satisfies the condition of 0.2≤x≤0.8.
According to claim 8,
The multilayer ceramic capacitor wherein the internal electrode includes a Ni component.
According to claim 8,
A multilayer ceramic capacitor further comprising 0.1 to 1.0 mol% of a first subcomponent that is an oxide or carbonate of at least one of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn, based on 100 mol% of the first and second main components. .
According to claim 10,
A multilayer ceramic capacitor further comprising 0.1 to 1.0 mol% of a second subcomponent that is an oxide or carbonate of at least one of Mg and Al relative to 100 mol% of the first and second main components.
According to claim 11,
A multilayer ceramic capacitor further comprising 0.1 to 1.0 mol% of a third subcomponent, which is an oxide or carbonate of at least one of Ce, Nb, La, and Sb, based on 100 mol% of the first and second main components.
According to claim 12,
A multilayer ceramic capacitor further comprising 0.1 to 1.0 mol% of a fourth subcomponent, which is an oxide or carbonate of at least one of Si, Ba, Ca, and Al, based on 100 mol% of the first and second main components.
According to claim 12,
A multilayer ceramic capacitor further comprising 0.1 to 1.0 mol% of a fourth subcomponent, which is a glass compound including Si, relative to 100 mol% of the first and second main components.

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