WO2024117710A1 - Dielectric composition having high-temperature stability and multilayer ceramic capacitor comprising same - Google Patents

Abstract

Disclosed is a dielectric composition comprising a barium titanate-based base material main component and minor components. The base material main component of the dielectric composition comprises a first main component represented by (Ba_1-xCa_x)TiO₃ and a second main component represented by (Ba_1-yCa_y)TiO₃, and the dielectric composition includes any one of oxides and carbonates of at least one of the elements Yb and Y among oxides and carbonates of the elements Mg, Si, V, Mn, Ba, Ca, Y, and Yb. A dielectric material formed by sintering the dielectric composition satisfies the X8R characteristics specified in the EIA standard.

Description

Dielectric composition having high temperature stability and multilayer ceramic capacitor containing the same

The present invention relates to a dielectric composition having high temperature stability and a multilayer ceramic capacitor including the same. In particular, the multilayer ceramic capacitor has X8R characteristics.

Multilayer ceramic chip capacitors have high capacity and reliability, but are relatively small in size and are widely used in fields that require precision and stability, such as automobiles and motors.

There are requirements for various factors such as capacity, temperature stability, and voltage stability for multilayer ceramic capacitors. In particular, since multilayer ceramic capacitors for automotive applications operate under high temperatures, their capacity (capacitance) must not change even at high temperatures. In this regard, the Electronic Industries Association (EIA) designates multilayer ceramic capacitors as It is stipulated that it is satisfactory.

The present invention provides a dielectric composition and a multilayer ceramic capacitor including the same.

The dielectric composition according to embodiments of the present invention includes a barium titanate-based base material main component and sub-components, wherein the base material main component includes a first main component expressed as (Ba _1-x Ca _x )TiO ₃ and (Ba _1-y Ca _y ) It includes a second main component expressed as TiO ₃ , wherein the sub-component includes a first sub-component containing at least one of oxide and carbonate of a valence fixed acceptor element including Mg, oxide of Si element, carbonate and glass. A second subcomponent containing at least one selected from the group, a third subcomponent containing at least one of oxides and carbonates of element V, and an valence containing at least one of Mn, Cr, Fe, Ni, Co, Cu, and Zn. A fourth subcomponent containing at least one selected from the group consisting of oxides and carbonates of variable acceptor elements, a fifth subcomponent containing at least one selected from the group consisting of oxides and carbonates of at least one element of Ba and Ca, and A sixth subcomponent containing at least one selected from the group consisting of oxides and carbonates of at least one element of Yb and Y; and at least one subcomponent, and the at least one subcomponent further includes the sixth subcomponent.

The dielectric composition according to embodiments of the present invention can be used to form a dielectric layer of a multilayer ceramic capacitor having a structure in which dielectric layers and internal electrode layers are alternately stacked.

The multilayer ceramic capacitor containing the dielectric composition of the present invention satisfies the X8R characteristics of the EIA standard.

Figure 1 shows a multilayer ceramic capacitor according to an embodiment of the present invention.

Figure 2 shows a multilayer ceramic capacitor according to an embodiment of the present invention.

Hereinafter, in order to explain in detail enough to enable those skilled in the art of the present invention to easily implement the technical idea of the present invention, the most preferred embodiments of the present invention will be described with reference to the accompanying drawings. . First, when adding reference numerals to components in each drawing, it should be noted that identical components are given the same reference numerals as much as possible even if they are shown in different drawings. Additionally, in describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted.

The present invention relates to a dielectric composition, and electronic components containing the dielectric composition include capacitors, inductors, piezoelectric elements, varistors, or thermistors. Hereinafter, a multilayer ceramic capacitor will be described as an example of the dielectric composition and electronic components.

Multilayer Ceramic Capacitors

1 and 2 show a multilayer ceramic capacitor according to an embodiment of the present invention. Referring to FIG. 1, a multilayer ceramic capacitor according to an embodiment of the present invention includes a dielectric 100, a first external electrode 220, and a second external electrode 240.

The dielectric 100 is composed of a rectangular parallelepiped having an upper surface, a lower surface, a first side, a second side opposite the first side, a third side, and a fourth side opposite the third side, and the first side is on the left side in the drawing. As an example, the second side is the right side in the drawing, the third side is the front in the drawing, and the fourth side is the rear in the drawing.

The dielectric 100 may include a plurality of dielectric sheets. A plurality of dielectric sheets may be stacked. Each dielectric sheet includes a dielectric composition and may be formed by sintering the dielectric composition.

The first external electrode 220 is an electrode disposed on the first side of the dielectric 100. The first external electrode 220 and the second external electrode 240 may be formed to extend from the first side of the dielectric 100 to the top, bottom, third, and fourth sides of the dielectric 100. The second external electrode 240 is an electrode disposed on the second side of the dielectric 100. The second external electrode 240 may be formed to extend from the second side of the dielectric 100 to the top, bottom, third, and fourth sides of the dielectric 100. At this time, the first external electrode 220 and the second external electrode 240 may be formed to face each other at a predetermined distance from the top, bottom, third, and fourth sides of the dielectric 100.

Referring to FIG. 2, the multilayer ceramic capacitor according to an embodiment of the present invention may further include a plurality of electrode units 300. At this time, the plurality of electrode units 300 are stacked to form a stack, and this stack is disposed inside the dielectric 100.

The plurality of electrode units 300 are stacked vertically in the drawing and disposed inside the dielectric 100. Each electrode unit 300 includes a first electrode set 320 and a second electrode set 340, and the first electrode set 320 and the second electrode set 340 are alternately stacked.

The first electrode set 320 is composed of a plate-shaped conductor formed in a rectangular shape. The first electrode set 320 is disposed inside the dielectric 100 to be biased toward the first side of the dielectric 100 . The first end of the first electrode set 320 is connected to the first external electrode 220 on the first side of the dielectric 100.

The second electrode set 340 is composed of a plate-shaped conductor formed in a rectangular shape. The second electrode set 340 is disposed inside the dielectric 100 to be biased toward the second side of the dielectric 100 . The first end of the second electrode set 340 is connected to the second external electrode 240 on the second side of the dielectric 100.

The first electrode set 320 and the second electrode set 340 are distributed and disposed on two adjacent dielectric sheets among the dielectric sheets included in the dielectric 100. The first electrode set 320 and the second electrode set 340 may partially overlap with the dielectric sheet 110 therebetween.

Dielectric composition and method of manufacturing the same

Hereinafter, the dielectric composition and its manufacturing method according to embodiments of the present invention will be described in detail. The dielectric composition may form the dielectric 100 described above. However, in order to avoid redundant explanation, content that overlaps with the above-described content will be omitted.

The dielectric composition according to embodiments of the present invention may include a base material containing a rare earth element. The main component of the base material may be a barium titanate-based compound containing Ba and Ti, and optionally, it may be a compound to which Ca is additionally added.

Additionally, the dielectric composition according to embodiments of the present invention additionally includes a subcomponent, and the subcomponent may include first to sixth subcomponents.

The dielectric composition according to embodiments of the present invention satisfies the

Base material main ingredients

Dielectric compositions according to embodiments of the present invention may include base material main components including Ba and Ti. According to embodiments, according to one embodiment of the invention, the base material main component is a first main component expressed as (Ba _1-x Ca _x )TiO ₃ (x≤0.01) and (Ba _1-y Ca _y )TiO ₃ (0.05) It includes the second principal component expressed as ≤y≤0.15). Here, x and y are 0 or more, and when each of x and y is 0, the first/second main component becomes BaTiO3.

The first main component and the second main component may be included in the dielectric composition as powder. For example, the first main component may be included in the dielectric composition as a first powder, and the second main ingredient may be included as a second powder.

Depending on embodiments, the mixing ratio of the first main component and the second main component may be z. That is, the molar ratio of the first main component and the second main component may be 1-z:z. At this time, z may be 0.2 to 0.6. For example, the mixture of the first main ingredient powder and the second main ingredient powder can be expressed as 1-z(Ba _1-x Ca _x )TiO ₃ + z(Ba _1-y Ca _y )TiO ₃ .

According to embodiments of the present invention, z, the mixing ratio of the first main component and the second main component, may satisfy the range of 0.2≤z≤0.6. Through this, crystal grains containing Ca are present in the sintered structure of dielectric compositions according to embodiments of the present invention, and the sizes and Ca contents of these crystal grains are mixed in various ways. Accordingly, the dielectric composition exhibits a relatively low change in capacitance even at high temperatures (eg, 150 degrees Celsius) and has the effect of having a low loss coefficient.

The main component of the base material may be included in powder form and included in the dielectric composition. The average particle diameter of the base material powder is not particularly limited, but may be 1000 nm or less. Preferably, the average particle diameter of the base material powder may be 200 nm to 350 nm, and more preferably 250 nm.

1st subingredient

The dielectric composition according to embodiments of the present invention may include one or more of an oxide and a carbonate of a fixed-valence acceptor element containing Mg as a first subcomponent.

The first subcomponent may be included in an amount of 2.0 mole parts or less based on 100 mole parts of the base material main ingredient. The content of the first subcomponent may be based on the content of the Mg element included in the first subcomponent, regardless of the type of addition such as oxide or carbonate. For example, the content of the Mg element included in the first subcomponent may be 2.0 mole parts or less based on 100 mole parts of the main component of the base material.

If the content of the first subcomponent exceeds 2.0 mole parts with respect to 100 mole parts of the dielectric base material main component, it is undesirable because the dielectric constant may be lowered and the high-temperature withstand voltage characteristics may be lowered.

Secondary ingredient

The dielectric composition according to embodiments of the present invention may include, as a second subcomponent, at least one selected from the group consisting of oxide of Si element, carbonate of Si element, and glass containing Si element.

The second subcomponent may be included in an amount of 1.5 to 4.0 mole parts based on 100 mole parts of the base material main component. The content of the second subcomponent may be based on the content of the Si element included in the second subcomponent, regardless of the type of addition such as glass, oxide, or carbonate.

If the content of the second subcomponent is less than 1 mole part per 100 mole parts of the main dielectric base material, the dielectric constant and high-temperature withstand voltage may be reduced, and if it is contained in excess of 4.5 mole parts, problems such as reduced sinterability and density, and secondary phase formation may occur. It may be undesirable.

Third ingredient

The dielectric composition according to embodiments of the present invention may include, as a third subcomponent, one or more of oxides containing V and carbonates thereof.

The third subcomponent may be included in an amount of 0.1 to 2 mole parts based on 100 mole parts of the base material main ingredient. The content of the third subcomponent can be based on the content of the V element included in the third subcomponent, regardless of the type of addition such as oxide or carbonate. For example, the content of element V included in the third subcomponent may be 0.1 to 2 mole parts or less based on 100 mole parts of the main component of the base material.

The third subcomponent plays a role in stabilizing the change in capacity at high temperatures. If the content of the third subcomponent is less than 0.1 mole compared to the base material main component, the RC value may be lowered, and if it exceeds 2 mole parts per 100 mole parts of the dielectric base material main component, the high temperature The withstand voltage may be lowered.

Fourth ingredient

The dielectric composition according to embodiments of the present invention contains, as a fourth subcomponent, at least one element selected from the group consisting of Mn, Cr, Fe, Ni, Co, Cu, and Zn, their oxides, and their carbonates. can do.

The fourth subcomponent may be included in an amount of 0.1 to 2 mole parts based on 100 mole parts of the base material main ingredient. The content of the fourth subcomponent may be based on the content of at least one element among Mn, Cr, Fe, Ni, Co, Cu, and Zn included in the fourth subcomponent, regardless of the type of addition such as oxide or carbonate. For example, the total content of at least one valence variable acceptor element among Mn, Cr, Fe, Ni, Co, Cu, and Zn contained in the fourth subcomponent may be 0.1 to 2 mole parts based on 100 mole parts of the base material main component. there is.

The fourth subcomponent serves to increase the IR value, and if the content of the fourth subcomponent is less than 0.1 mole part, the IR characteristics may deteriorate and reliability may decrease. Additionally, if the content of the fourth subcomponent exceeds 2 molar parts, the high temperature accelerated life may be reduced.

Fifth subingredient

The dielectric composition according to embodiments of the present invention may include, as a fifth subcomponent, at least one selected from the group consisting of oxides and carbonates of one or more of the elements Ba and Ca.

The fifth subcomponent may be included in an amount of 2 to 4.5 mole parts based on 100 mole parts of the base material main ingredient. The content of the fifth subcomponent may be based on the sum of the contents of one or more of the Ba and Ca elements included in the fifth subcomponent, regardless of the type of addition such as oxide or carbonate. For example, the sum of the contents of one or more of the Ba and Ca elements included in the fifth subcomponent may be 2 to 4.5 mole parts based on 100 mole parts of the base material main component.

When the fifth subcomponent is included in an amount of 2 to 4.5 mole parts based on 100 mole parts of the main component of the base material, high-temperature withstand voltage characteristics are improved and the capacitance change at high temperature can be stabilized.

6th subingredient

The dielectric composition according to embodiments of the present invention may include, as a sixth subcomponent, at least one selected from the group consisting of oxides and carbonates of at least one of Yb and Y elements. Alternatively, the sixth subcomponent includes one or more selected from the group consisting of oxides and carbonates of one or more of Dy, Ho, Sm, Gd, Er, La, Ce and Nd, which are other rare earth elements in place of Yb and Y elements. You may.

The sixth subcomponent may be included in an amount of 2 to 4 mole parts based on 100 mole parts of the base material main ingredient. The content of the sixth subcomponent can be based on the content of the element included in the sixth subcomponent without distinguishing the form of addition such as oxide or carbonate. For example, the total content of elements included in the sixth subcomponent may be 2 to 4 molar parts based on 100 molar parts of the base material main component.

The sixth subcomponent serves to prevent a decrease in reliability of the multilayer ceramic capacitor formed with the dielectric composition according to embodiments of the present invention.

If the content of the sixth subcomponent is less than 2 mole parts with respect to 100 mole parts of the main component of the base material, the effect of improving the TCC (temperature coefficient of capacitance) of the high temperature part may not be significant, and if the content of the sixth subcomponent exceeds 4 mole parts with respect to 100 mole parts of the main component of the base material. Doing so may deteriorate the high-temperature withstand voltage characteristics.

Experiment example

1 _- z ₍ Ba _{1 - x Ca}

Starting materials are BaCO ₃ , TiO ₂ and It is CaCO ₃ . These starting raw material powders were mixed in a ball mill and calcined in the range of 900 to 1000°C to produce (Ba _1-x Ca _x )TiO ₃ first main ingredient powder and (Ba _1-y Ca _y )TiO ₃ second main ingredient powder with a particle size of 250 nm. prepared.

After adding the secondary ingredient additive powder to the first main ingredient powder and the second main ingredient powder according to the composition ratio, the raw material powder containing the main ingredient and secondary ingredient is mixed with ethanol/toluene, dispersant, and binder using a zirconia ball as a mixing/dispersing media. , ball milling was performed for a predetermined period of time (e.g., 20 hours).

The prepared slurry was used to manufacture a molded sheet with a thickness of 10 ㎛ using a doctor blade type coater. Internal electrodes were printed on the molded sheet. The upper and lower covers were manufactured by stacking 25 layers of cover sheets, and 21 layers of printed active sheets were stacked while pressing to create a pressed bar. The pressed bar was cut into chips of size 3225 (length x width x thickness 3.2 mm x 2.5 mm x 2.5 mm) using a cutter.

After calcining the manufactured chip, it is fired in a reducing atmosphere (0.1% H ₂ /99.9% N ₂ , H ₂ O/H ₂ /N ₂ atmosphere) at a temperature of 1250 to 1350°C for more than 1 hour, and then at 1000°C. Heat treatment was performed by re-oxidation in a nitrogen (N2) atmosphere for more than 2 hours.

External electrodes were completed on the fired chip through a termination process and electrode firing using conductive paste.

Capacitance (dielectric constant), change in capacitance with temperature (TCC), and high-temperature withstand voltage were measured and evaluated for the multilayer ceramic capacitor specimen completed as described above. In addition, room temperature insulation resistance, high temperature acceleration life, and loss coefficient were evaluated, but are not described.

Room temperature capacitance was measured using an LCR-meter under the conditions of 1 kHz and AC 0.2 V/㎛. The dielectric constant of the multilayer ceramic capacitor (MLCC) chip was calculated from the capacitance, dielectric thickness, internal electrode area, and number of layers of the multilayer ceramic capacitor (MLCC) chip.

The change in capacitance according to temperature was measured in the temperature range from -55℃ to 150℃. In the corresponding temperature range, the change in capacity was measured at 1kHz and 1Vrms using an LCR-meter. At this time, the rate of change (%) of capacitance at each temperature compared to the capacitance at 25°C is measured. In this specification, the change in capacitance at 150°C is described.

High-temperature withstand voltage was measured by applying a voltage step of DC 5 V/㎛ for 10 minutes at 150°C and continuously increasing this voltage step, and the voltage at which IR withstood more than 100GΩ was measured. If the high-temperature withstand voltage was more than 50 V/μm, it was judged as good, and if it was less than 40 V/μm, it was judged as bad.

The RC value was judged as good if it was over 1000, and bad if it was less than 1000.

Sample	Main ingredient 1	Main ingredient 2	mix molar ratio	Number of moles of minor ingredients per 100 moles of main ingredient								additive ratio
	(Ba 1-x Ca x )TiO 3	(Ba 1-y Ca y )TiO 3		One	2	3	4	5		6		(Ba+Ca+Yb+Y)/Si
	x	y	z	MgCO 3	SiO 2	V 2 O 5	MnO 2	CaCO 3	BaCO 3	Y 2 O 3	Yb 2 O 3
One	0.01	0.02	0.2	1.45	2.69	0.06	0.35	2.00	1.65	0.3	1.09	2.39
2	0.01	0.02	0.6	1.45	2.69	0.06	0.35	2.00	1.65	0.3	1.09	2.39
3	0.01	0.05	0.1	1.45	2.69	0.06	0.35	2.00	1.65	0.3	1.09	2.39
4	0.01	0.05	0.2	1.45	2.69	0.06	0.35	2.00	1.65	0.3	1.09	2.39
5	0.01	0.05	0.6	1.45	2.69	0.06	0.35	2.00	1.65	0.3	1.09	2.39
6	0.01	0.05	0.7	1.45	2.69	0.06	0.35	2.00	1.65	0.3	1.09	2.39
7	0.01	0.15	0.2	1.45	2.69	0.06	0.35	2.00	1.65	0.3	1.09	2.39
8	0.01	0.15	0.6	1.45	2.69	0.06	0.35	2.00	1.65	0.3	1.09	2.39
9	0.01	0.2	0.2	1.45	2.69	0.06	0.35	2.00	1.65	0.3	1.09	2.39
10	0.01	0.2	0.6	1.45	2.69	0.06	0.35	2.00	1.65	0.3	1.09	2.39
11	0.02	0.2	0.2	1.45	2.69	0.06	0.35	2.00	1.65	0.3	1.09	2.39
12	0.02	0.2	0.6	1.45	2.69	0.06	0.35	2.00	1.65	0.3	1.09	2.39

Sample	permittivity	High temperature TCC (150℃)	RC value	High temperature (150℃) Withstand voltage (V/μm)	Trait Judgment
One	2530	-19.8	Good	Good	X
2	2481	-18.6	Good	Good	X
3	2457	-17.5	Good	Good	X
4	2439	-13.8	Good	Good	O
5	2412	-13.5	Good	Good	O
6	2397	-13.1	error	Good	X
7	2297	-12.9	Good	Good	O
8	2271	-13.1	Good	Good	O
9	2173	-12.7	error	Good	X
10	2131	-12.5	error	Good	X
11	2377	-17.2	Good	Good	X
12	2327	-16.8	Good	Good	X

Samples 1 to 12 in Table 1 have a content of 1.45 moles of the first subcomponent Mg, 2.69 moles of the second subcomponent Si, 0.12 moles of the third subcomponent V, 0.35 moles of the fourth subcomponent Mn, and 0.35 moles of the fifth subcomponent. With the sum of the contents of (Ca, Ba) fixed at 3.65 mol and the sum of the contents of the sixth subcomponents (Y, Yb) fixed at 2.78, the Ca content of the first main component, the Ca content of the second main component, and the first main component and It represents samples in which the mixing molar ratio of the second main component was changed, and Samples 1 to 12 in Table 2 show the characteristics of the samples corresponding to Samples 1 to 12 in Table 1.

Meanwhile, for samples 1 to 10, the Ca content x of the first main component is 0.01, and for samples 11 to 12, the Ca content x of the first main component is 0.02.

When the Ca content y of the second main component is 0.05 or less (e.g., 0.02) and the mixing molar ratio z is 0.2 and 0.6 (samples 1 and 2), the TCC of the high temperature part exceeds 15%, making it vulnerable to temperature changes.

In addition, even if the Ca content y of the second main component is 0.05, even when the mixing molar ratio z is less than 0.2 (e.g., 0.1) (Sample 3), the TCC of the high temperature part exceeds 15%, and the Ca content y of the second main component is If it exceeds 0.6 (eg, 0.7) (Sample 6), the RC value becomes less than 1000, which reduces reliability.

In addition, even when the Ca content y of the second main component exceeds 0.15 (e.g., 0.2) and the mixing molar ratio z is 0.2 to 0.6 (Samples 9 and 10), the RC value is less than 1000, resulting in lower reliability.

In addition, when the Ca content x of the first main component exceeds 0.01 (e.g., 0.02), even if the Ca content y of the second main component is 0.05 to 0.15 and the mixing molar ratio z is 0.2 to 0.6 (Samples 11 and 12) , the TCC of the high temperature part deviates from 15%.

In conclusion, when the Ca content x of the first main component is 0.01 or less, the Ca content y of the second main component is 0.05 to 0.15, and the mixing molar ratio z is 0.2 to 0.6 (samples 4, 5, 7 and 8) The high-temperature TCC satisfies the X8R standard within ±15%, and good RC characteristics of over 1000 can be achieved. Therefore, it can be said that the content x of the first main component is 0.01 or less, the content y of the second main ingredient is 0.05 to 0.15, and the mixing molar ratio z is 0.2 to 0.6.

Sample	Main ingredient 1	Main ingredient 2	mix molar ratio	Number of moles of minor ingredients per 100 moles of main ingredient								additive ratio
	(Ba 1-x Ca x )TiO 3	(Ba 1-y Ca y )TiO 3		One	2	3	4	5		6		(Ba+Ca+Yb+Y)/Si
	x	y	z	MgCO 3	SiO 2	V 2 O 5	MnO 2	CaCO 3	BaCO 3	Y 2 O 3	Yb 2 O 3
13	0.005	0.1	0.4	1.45	2.69	0.06	0.35	-	1.0	0.3	1.09	1.41
14	0.005	0.1	0.4	1.45	2.69	0.06	0.35	-	2	0.3	1.09	1.67
15	0.005	0.1	0.4	1.45	2.69	0.06	0.35	-	4.5	0.3	1.09	3.16
16	0.005	0.1	0.4	1.45	2.69	0.06	0.35	-	5	0.3	1.09	3.72
17	0.005	0.1	0.4	1.45	2.69	0.06	0.35	1.0	-	0.3	1.09	1.41
18	0.005	0.1	0.4	1.45	2.69	0.06	0.35	2	-	0.3	1.09	1.67
19	0.005	0.1	0.4	1.45	2.69	0.06	0.35	4.5	-	0.3	1.09	3.16
20	0.005	0.1	0.4	1.45	2.69	0.06	0.35	5	-	0.3	1.09	3.72

Sample	permittivity	High temperature TCC (150℃)	RC value	High temperature (150℃) Withstand voltage (V/μm)	Trait Judgment
13	3321	-18.7	Good	error	X
14	2513	-13.7	Good	Good	O
15	2463	-13.5	Good	Good	O
16	2213	-16.8	error	error	X
17	3311	-19.2	Good	error	X
18	2491	-14.1	Good	Good	O
19	2473	-13.9	Good	Good	O
20	2133	-17.2	error	error	X

Samples 13 to 20 in Table 3 have a Ca content x of the first main component of 0.05, a Ca content y of the second main component of 0.1, a content of the first subcomponent Mg of 1.45 mol, and a content of the second subcomponent Si of 2.69 mol. Mol, with the content of the third subcomponent V being 0.12 mole, the content of the fourth subcomponent Mn being 0.35 mole, and the sum of the contents of the sixth subcomponent (Y, Yb) being fixed at 2.78, the content of the fifth subcomponent (Ca, Ba) indicates samples that have changed, and samples 13 to 20 in Table 4 show the characteristics of the samples corresponding to samples 13 to 20 in Table 3.

When the content of the fifth subcomponent Ba is less than 2 mol (e.g., 1.0 mol) (sample 13), the dielectric constant increases to over 3,000 and the high temperature TCC (150°C) deviates from ±15%, making it vulnerable to temperature changes. In addition, when the content of the fifth subcomponent Ba exceeds 4.5 mol (sample 16), the high temperature TCC (150°C) deviates from ±15% and both the RC value and high temperature withstand voltage values are defective.

When the content of the fifth subcomponent Ba is 2 to 4.5 mol (Samples 14 and 15), the high temperature TCC satisfies the . In addition, Samples 17 to 20 are obtained by replacing the fifth subcomponent Ba with Ca in Samples 13 to 16, and it can be confirmed that the dielectric constant, RC value, high temperature TCC and high temperature withstand voltage characteristics are substantially the same.

Therefore, it can be said that the appropriate range of the sum of the contents of the fifth subcomponent (Ba, Ca) is 2 to 4.5 mole for 100 mole parts of the main component of the base material.

Sample	Main ingredient 1	Main ingredient 2	mix molar ratio	Number of moles of minor ingredients per 100 moles of main ingredient								additive ratio
	(Ba 1-x Ca x )TiO 3	(Ba 1-y Ca y )TiO 3		One	2	3	4	5		6		(Ba+Ca+Yb+Y)/Si
	x	y	z	MgCO 3	SiO 2	V 2 O 5	MnO 2	CaCO 3	BaCO 3	Y 2 O 3	Yb 2 O 3
21	0.005	0.1	0.4	1.45	2.69	0.06	0.35	2.00	1.65	-	0.5	1.73
22	0.005	0.1	0.4	1.45	2.69	0.06	0.35	2.00	1.65	-	One	2.10
23	0.005	0.1	0.4	1.45	2.69	0.06	0.35	2.00	1.65	-	2	2.84
24	0.005	0.1	0.4	1.45	2.69	0.06	0.35	2.00	1.65	-	2.5	3.22
25	0.005	0.1	0.4	1.45	2.69	0.06	0.35	2.00	1.65	One	-	2.10
26	0.005	0.1	0.4	1.45	2.69	0.06	0.35	2.00	1.65	2	-	2.84
27	0.005	0.1	0.4	1.45	2.69	0.06	0.35	2.00	1.65	2.5	-	3.22

Sample	permittivity	High temperature TCC (150℃)	RC value	High temperature (150℃) Withstand voltage (V/μm)	Trait Judgment
21	2611	-18.7	Good	Good	X
22	2587	-13.7	Good	Good	O
23	2491	-13.5	Good	Good	O
24	2367	-12.9	Good	error	X
25	3311	-19.2	Good	error	X
26	2491	-14.1	Good	Good	O
27	2473	-13.9	Good	Good	O

Samples 21 to 27 in Table 5 have a Ca content x of the first main component of 0.05, a Ca content y of the second main component of 0.1, a content of the first subcomponent Mg of 1.45 mol, and a content of the second subcomponent Si of 2.69 mol. Mol, with the content of the third subcomponent V fixed at 0.12 mole, the content of the fourth subcomponent Mn at 0.35 mole, and the sum of the contents of the fifth subcomponent (Ca, Ba) fixed at 3.65 mole, the content of the sixth subcomponent (Y, Yb) The changed samples are shown, and samples 21 to 27 in Table 6 show the characteristics of the samples corresponding to samples 21 to 27 in Table 5.

When the content of the sixth subcomponent Yb is 0 mol (sample 21), the high temperature TCC (150°C) deviates from ±15%, making it vulnerable to temperature changes. In addition, when the content of the sixth subcomponent Yb exceeds 4 mol (sample 24), the high temperature TCC (150°C) does not exceed ±15%, but there is a problem of poor high temperature withstand voltage characteristics.

In the range where the content of the sixth subcomponent Yb exceeds 0 mole and is less than 4 mole (samples 22 to 23), the high temperature TCC satisfies the X8R standard within ±15%, and good high temperature withstand voltage characteristics of 50V/μm or more are possible. In addition, samples 24 to 27 are obtained by replacing the sixth subcomponent Yb with Y in samples 21 to 23, and it can be confirmed that the dielectric constant, RC value, high temperature TCC and high temperature withstand voltage characteristics are substantially the same.

Therefore, the appropriate content range of the sixth subcomponent (Y, Yb) can be said to be more than 0 and less than 4 mole parts in element ratio for 100 mole parts of the main component of the base material.

Sample	Main ingredient 1	Main ingredient 2	mix molar ratio	Number of moles of minor ingredients per 100 moles of main ingredient								additive ratio
	(Ba 1-x Ca x )TiO 3	(Ba 1-y Ca y )TiO 3		One	2	3	4	5		6		(Ba+Ca+Yb+Y)/Si
	x	y	z	MgCO 3	SiO 2	V 2 O 5	MnO 2	CaCO 3	BaCO 3	Y 2 O 3	Yb 2 O 3
28	0.005	0.1	0.4	1.45	1.5	0.06	0.35	2.00	2.00	0.75	1.20	5.27
29	0.005	0.1	0.4	1.45	1.7	0.06	0.35	2.00	1.65	0.75	1.20	4.64
30	0.005	0.1	0.4	1.45	4	0.06	0.35	1.00	1.00	0.4	0.6	1.00
31	0.005	0.1	0.4	1.45	3.8	0.06	0.35	1.00	1.00	0.4	0.6	1.06
32	0.005	0.1	0.4	1.45	One	0.06	0.35	1.00	1.00	0.5	1.3	5.6
33	0.005	0.1	0.4	1.45	One	0.06	0.35	1.00	1.00	0.35	0.9	4.5
34	0.005	0.1	0.4	1.45	4	0.06	0.35	1.00	1.00	0.35	0.65	One
35	0.005	0.1	0.4	1.45	4	0.06	0.35	1.00	1.00	0.4	0.75	1.075

Sample	permittivity	High temperature TCC (150℃)	RC value	High temperature (150℃) Withstand voltage (V/μm)	Trait Judgment
28	2717	-17.3	Good	error	X
29	2617	-13.7	Good	Good	O
30	2403	-16.5	Good	Good	X
31	2481	-14.1	Good	Good	O
32	2717	-16.4	Good	Good	X
33	2591	-14.8	Good	Good	O
34	2371	-16.1	Good	Good	X
35	2291	-14.7	Good	Good	O

Samples 28 to 35 in Table 7 have a Ca content Mol, with the content of the fourth subcomponent Mn fixed at 0.35 mol, the additive ratio (Ba+Ca+Yb) is changed by changing the contents of the second subcomponent Si, the fifth subcomponent (Ca, Ba), and the sixth subcomponent (Y, Yb). It represents samples in which the ratio of +Y)/Si was varied, and samples 28 to 35 in Table 8 show the characteristics of the samples corresponding to samples 28 to 35 in Table 5.

Even if the contents of the second subcomponent Si, the fifth subcomponent (Ca, Ba), and the sixth subcomponent (Y, Yb) are within the above-mentioned appropriate range, the additive ratio (Ba+Ca+Yb+Y)/Si is less than 1.05 or (Samples 30, 34) or exceeding 4.64 (Samples 28, 32), the high-temperature TCC deviates from ±15%, making it vulnerable to temperature changes or having poor high-temperature withstand voltage characteristics.

Therefore, the appropriate range of the additive ratio (Ba+Ca+Yb+Y)/Si can be said to be 1.05 to 4.64. This fact can also be confirmed through the samples 1 to 27 described above.

The present invention is not limited by the above-described embodiments and attached drawings, but is limited by the attached claims. Therefore, it will be apparent to those skilled in the art that various forms of substitution, modification, and change are possible without departing from the technical spirit of the present invention as set forth in the claims, and this is also subject to the appended claims. It may be said to belong to the technical idea described in .

Claims (13)

1. In a dielectric composition containing a barium titanate-based base material main component and auxiliary components,

   The base material main component includes a first main component expressed as (Ba _1-x Ca _x )TiO ₃ and a second main component expressed as (Ba _1-y Ca _y )TiO ₃ ,

   The above subingredients are:

   a first subcomponent comprising at least one of an oxide and a carbonate of a valence fixed acceptor element comprising Mg;

   A second subcomponent containing at least one selected from the group consisting of oxides, carbonates, and glasses of Si element;

   a third subcomponent comprising one or more of oxides and carbonates of element V;

   A fourth subcomponent comprising at least one selected from the group consisting of oxides and carbonates of variable-valence acceptor elements including one or more of Mn, Cr, Fe, Ni, Co, Cu, and Zn;

   A fifth subcomponent containing at least one selected from the group consisting of oxides and carbonates of at least one element of Ba and Ca; and

   A sixth subcomponent containing at least one selected from the group consisting of oxides and carbonates of at least one element of Yb and Y; Contains at least one accessory ingredient of,

   The at least one subcomponent further includes the sixth subcomponent,

   Dielectric composition.
2. According to paragraph 1,

   The Ca content x of the first main component is 0.01 or less,

   Dielectric composition.
3. According to paragraph 1,

   The Ca content y of the second main component is 0.05 to 0.15,

   Dielectric composition.
4. According to paragraph 1,

   When the mixing molar ratio of the first main component and the second main ingredient is 1-z:z, z is 0.2 to 0.6.

   Dielectric composition.
5. According to paragraph 1,

   The at least one subcomponent further includes the first subcomponent,

   The content of the Mg element contained in the first subcomponent is 2 mole parts or less with respect to 100 mole parts of the base material main component,

   Dielectric composition.
6. According to paragraph 1,

   The at least one subcomponent further includes the second subcomponent,

   The content of the Si element contained in the second subcomponent is 1.5 to 4.0 mole parts with respect to 100 mole parts of the base material main component,

   Dielectric composition.
7. According to paragraph 1,

   The at least one subcomponent further includes the third subcomponent,

   The content of the V element contained in the third subcomponent is 0.1 to 2 mole parts per 100 mole parts of the base material main component,

   Dielectric composition.
8. According to paragraph 1,

   The at least one subcomponent further includes the fourth subcomponent,

   The sum of the contents of the variable valence acceptor elements contained in the fourth subcomponent is 0.1 to 2 mole parts with respect to 100 mole parts of the base material main component,

   Dielectric composition.
9. According to paragraph 1,

   The at least one subcomponent further includes the fifth subcomponent,

   The content of one or more elements included in the fifth subcomponent is 2 to 4.5 mole parts with respect to 100 mole parts of the base material main component,

   Dielectric composition.
10. According to paragraph 1,

    The content of one or more elements included in the sixth subcomponent is 2 to 4 molar parts with respect to 100 molar parts of the base material main component,

    Dielectric composition.
11. According to paragraph 1,

    The at least one subcomponent further includes the second subcomponent and the fifth subcomponent,

    Dielectric composition.
12. According to clause 11,

    The subcomponent ratio (Ba+Ca+Yb+Y)/Si, defined as the ratio of the Si element contained in the second subcomponent, one or more elements contained in the fifth subcomponent, and one or more elements contained in the sixth subcomponent, is 1.05. to 4.64,

    Dielectric composition.
13. A multilayer ceramic capacitor having a structure in which dielectric layers and internal electrode layers are alternately laminated, wherein the dielectric layer includes a barium titanate-based base material main component and at least a minor component,

    The base material main component includes a first main component expressed as (Ba _1-x Ca _x )TiO ₃ and a second main component expressed as (Ba _1-y Ca _y )TiO ₃ ,

    The above subingredients are:

    a first subcomponent comprising at least one of an oxide and a carbonate of a valence fixed acceptor element comprising Mg;

    A second subcomponent containing at least one selected from the group consisting of oxides, carbonates, and glasses of Si element;

    a third subcomponent comprising one or more of oxides and carbonates of element V;

    A fourth subcomponent comprising at least one selected from the group consisting of oxides and carbonates of variable-valence acceptor elements including one or more of Mn, Cr, Fe, Ni, Co, Cu, and Zn;

    A fifth subcomponent containing at least one selected from the group consisting of oxides and carbonates of at least one element of Ba and Ca; and

    A sixth subcomponent containing at least one selected from the group consisting of oxides and carbonates of at least one element of Yb and Y; Contains at least one accessory ingredient of,

    The at least one subcomponent further includes the sixth subcomponent,

    Multilayer ceramic capacitors.

Images