阅读说明：本技术 介电材料及使用该介电材料的多层陶瓷电子组件 (Dielectric material and multilayer ceramic electronic component using the same ) 是由 尹硕晛 金东勳 金珍友 于 2021-05-21 设计创作，主要内容包括：本公开提供一种介电材料及使用该介电材料的多层陶瓷电子组件,所述介电材料包括：主成分,由(Ba-(1-x)Ca-(x))(Ti-(1-y)Zr-(y))O-(3)、(Ba-(1-x)Ca-(x))(Ti-(1-)-(y)Sn-(y))O-(3)或(Ba-(1-x)Ca-(x))(Ti-(1-y)Hf-(y))O-(3)(0≤x≤1且0≤y≤0.05)表示；以及副成分。当在使用Cu Kα1辐射(波长)的X射线衍射(XRD)图谱的(002)和(200)面的峰中,对应于最大峰的角度被称为θ-(0)并且对应于半峰全宽(FWHM)的角度分别被称为θ-(1)和θ-(2)(θ-(1)<θ-(2))时,(θ-(2)-θ-(0))/(θ-(0)-θ-(1))大于0.54且小于或等于1.0。(The present disclosure provides a dielectric material and a multilayer ceramic electronic component using the same, the dielectric material including: a main component of (Ba) 1‑x Ca x )(Ti 1‑y Zr y )O 3 、(Ba 1‑x Ca x )(Ti 1‑ y Sn y )O 3 Or (Ba) 1‑x Ca x )(Ti 1‑y Hf y )O 3 (0. ltoreq. x.ltoreq.1 and 0. ltoreq. y.ltoreq.0.05); and subcomponents. When Cu Ka 1 radiation (wavelength) is used ) X-ray ofOf the peaks of the (002) and (200) planes of the line diffraction (XRD) pattern, the angle corresponding to the largest peak is called θ 0 And angles corresponding to a full width at half maximum (FWHM) are respectively referred to as θ 1 And theta 2 (θ 1 <θ 2 ) When (theta) 2 ‑θ 0 )/(θ 0 ‑θ 1 ) Greater than 0.54 and less than or equal to 1.0.)

1. A dielectric material, comprising:

a main component of (Ba)_1-xCa_x)(Ti_1-yZr_y)O₃、(Ba_1-xCa_x)(Ti_1-ySn_y)O₃Or (Ba)_1-xCa_x)(Ti_1-yHf_y)O₃Wherein 0. ltoreq. x.ltoreq.1 and 0. ltoreq. y.ltoreq.0.05, and

the auxiliary components of the composition are as follows,

wherein the application hasIn the peaks of (002) and (200) planes of the X-ray diffraction pattern of Cu Ka 1 radiation of wavelength λ of (theta)₂-θ₀)/(θ₀-θ₁) Greater than 0.54 and smallIs equal to or greater than 1.0, wherein θ₀Is the angle corresponding to the maximum peak, and θ₁And theta₂Are respectively angles corresponding to the full width at half maximum, where θ₁<θ₂。

2. The dielectric material of claim 1, wherein the dielectric material comprises grains and grain boundaries.

3. The dielectric material of claim 1, wherein the subcomponent comprises at least one of a first subcomponent, a second subcomponent, a third subcomponent, a fourth subcomponent, a fifth subcomponent and a sixth subcomponent, wherein:

the first subcomponent includes a compound of at least one element selected from variable valence acceptor elements including Mn, V, Cr, Fe, Ni, Co, Cu, and Zn;

the second sub-component contains a compound of at least one element selected from fixed-valence acceptor elements containing Mg;

the third subcomponent includes a compound of at least one element selected from elements including Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb;

the fourth subcomponent includes a compound of at least one element selected from elements including Ba and Ca;

the fifth subcomponent comprises at least one compound selected from the group consisting of: oxides of the element Si, carbonates of the element Si, and glasses containing the element Si; and is

The sixth subcomponent includes a compound of at least one element selected from elements including Na and Li.

4. The dielectric material according to claim 1, wherein the subcomponent comprises a first subcomponent including a compound of at least one element selected from variable valence acceptor elements including Mn, V, Cr, Fe, Ni, Co, Cu, and Zn, and

the first subcomponent is contained in a range of greater than or equal to 0.1 molar part and less than or equal to 1.0 molar part based on 100 molar parts of the main component.

5. The dielectric material according to claim 1, wherein the subcomponent comprises a second subcomponent comprising a compound of at least one element selected from fixed-valence acceptor elements including Mg, and

the second subcomponent is contained in a range of less than or equal to 2.0 molar parts based on 100 molar parts of the main component.

6. The dielectric material according to claim 1, wherein the subcomponent comprises a third subcomponent comprising a compound of at least one element selected from elements including Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd and Yb, and

the third subcomponent is contained in a range of greater than or equal to 0.3 molar part and less than or equal to 5.4 molar parts based on 100 molar parts of the main component.

7. The dielectric material according to claim 1, wherein the subcomponent comprises a fourth subcomponent comprising a compound of at least one element selected from elements including Ba and Ca, and

the fourth subcomponent is contained in an amount of 5.0 parts by mole or less based on 100 parts by mole of the main component.

8. The dielectric material of claim 1, wherein the subcomponent comprises a fifth subcomponent comprising at least one selected from the group consisting of: an oxide of an element Si, a carbonate of an element Si and a glass containing an element Si, and

the fifth subcomponent is contained in a range of greater than or equal to 0.5mol parts and less than or equal to 5.0 mol parts based on 100 mol parts of the main component.

9. The dielectric material according to claim 1, wherein the subcomponent comprises a sixth subcomponent comprising a compound of at least one element selected from elements including Na and Li, and

the sixth subcomponent is contained in an amount of less than or equal to 1.0 molar part based on 100 molar parts of the main component.

10. The dielectric material of claim 1, wherein the subcomponents of the multilayer ceramic electronic component include a third subcomponent, a fourth subcomponent, and a fifth subcomponent, wherein:

the third subcomponent includes a compound of at least one element selected from elements including Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb;

the fourth subcomponent includes a compound of at least one element selected from elements including Ba and Ca; and is

The fifth subcomponent comprises at least one compound selected from the group consisting of: an oxide of an element Si, a carbonate of an element Si and a glass containing an element Si, and

when the X-axis represents the number of moles of the fifth subcomponent and the Y-axis represents the sum of the number of moles of the third subcomponent and the fourth subcomponent based on 100 mole parts of the main component, the relationship among the number of moles of the third subcomponent, the fourth subcomponent and the fifth subcomponent belongs to the boundary or inside of a quadrangle connecting point a (0.500, 1.900), point B (0.500, 3.10), point C (5.000, 5.400) and point D (5.000, 3.900).

11. A multilayer ceramic electronic component comprising:

a ceramic body including a dielectric layer, a first internal electrode, and a second internal electrode; and

first and second external electrodes respectively disposed on outer surfaces of the ceramic main body and connected to the first and second internal electrodes respectively,

wherein the dielectric layerComprises (Ba)_1-xCa_x)(Ti_1-yZr_y)O₃、(Ba_1-xCa_x)(Ti_1-ySn_y)O₃Or (Ba)_1-xCa_x)(Ti_1-yHf_y)O₃A main component and a subcomponent represented by the formula (I), wherein x is 0. ltoreq. x.ltoreq.1 and y is 0. ltoreq. y.ltoreq.0.05, and

in use hasIn the peaks of (002) and (200) planes of the X-ray diffraction pattern of Cu Ka 1 radiation of wavelength λ of (theta)₂-θ₀)/(θ₀-θ₁) Greater than 0.54 and less than or equal to 1.0, wherein θ₀Is the angle corresponding to the maximum peak, and θ₁And theta₂Are respectively angles corresponding to the full width at half maximum, where θ₁<θ₂。

12. The multilayer ceramic electronic component of claim 11, wherein the subcomponents comprise at least one of first, second, third, fourth, fifth and sixth subcomponents:

the first subcomponent includes a compound of at least one element selected from variable valence acceptor elements including Mn, V, Cr, Fe, Ni, Co, Cu, and Zn;

the second sub-component contains a compound of at least one element selected from fixed-valence acceptor elements containing Mg;

the third subcomponent includes a compound of at least one element selected from elements including Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb;

the fourth subcomponent includes a compound of at least one element selected from elements including Ba and Ca;

the fifth subcomponent comprises at least one compound selected from the group consisting of: oxides of the element Si, carbonates of the element Si, and glasses containing the element Si; and is

The sixth subcomponent includes a compound of at least one element selected from elements including Na and Li.

13. The multilayer ceramic electronic component of claim 11, wherein the subcomponents of the multilayer ceramic electronic component include a third subcomponent, a fourth subcomponent, and a fifth subcomponent, wherein:

the third subcomponent includes a compound of at least one element selected from elements including Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb;

the fourth subcomponent includes a compound of at least one element selected from elements including Ba and Ca; and is

The fifth subcomponent comprises at least one compound selected from the group consisting of: an oxide of an element Si, a carbonate of an element Si and a glass containing an element Si, and

wherein, when the X-axis represents the number of moles of the fifth subcomponent and the Y-axis represents the sum of the number of moles of the third subcomponent and the fourth subcomponent based on 100 parts by mole of the main component, the relationship among the number of moles of the third subcomponent, the fourth subcomponent and the fifth subcomponent belongs to the boundary or inside of a quadrangle connecting point a (0.500, 1.900), point B (0.500, 3.10), point C (5.000, 5.400) and point D (5.000, 3.900).

14. The multilayer ceramic electronic component of claim 11, wherein (θ)₂-θ₀)/(θ₀-θ₁) Greater than or equal to 0.56.

15. The multilayer ceramic electronic component of claim 11, wherein (θ)₂-θ₀)/(θ₀-θ₁) Greater than or equal to 0.58.

16. The multilayer ceramic electronic component of claim 11, wherein (θ)₂-θ₀)/(θ₀-θ₁) Less than 1.0.

17. A dielectric material, comprising:

from (Ba)_1-xCa_x)(Ti_1-yZr_y)O₃、(Ba_1-xCa_x)(Ti_1-ySn_y)O₃Or (Ba)_1-xCa_x)(Ti_1-yHf_y)O₃A main component represented by (i) wherein 0. ltoreq. x.ltoreq.1 and 0. ltoreq. y.ltoreq.0.05, and

subcomponents including a third subcomponent, a fourth subcomponent and a fifth subcomponent,

the third subcomponent includes a compound of at least one element selected from elements including Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb;

the fourth subcomponent includes a compound of at least one element selected from elements including Ba and Ca; and is

The fifth subcomponent comprises at least one compound selected from the group consisting of: an oxide of an element Si, a carbonate of an element Si and a glass containing an element Si, and

when the X-axis represents the number of moles of the fifth subcomponent and the Y-axis represents the sum of the number of moles of the third subcomponent and the fourth subcomponent based on 100 mole parts of the main component, the relationship among the number of moles of the third subcomponent, the fourth subcomponent and the fifth subcomponent belongs to the boundary or inside of a quadrangle connecting point a (0.500, 1.900), point B (0.500, 3.10), point C (5.000, 5.400) and point D (5.000, 3.900).

18. The dielectric material of claim 17, wherein the subcomponent further comprises a first subcomponent,

wherein the first subcomponent includes a compound of at least one element selected from variable valence acceptor elements including Mn, V, Cr, Fe, Ni, Co, Cu, and Zn.

19. The dielectric material of claim 17, wherein the subcomponent further comprises a second subcomponent,

wherein the second sub-component contains a compound of at least one element selected from fixed-valence acceptor elements containing Mg.

20. The dielectric material of claim 18, wherein the dielectric material has a composition comprisingIn the peaks of (002) and (200) planes of the X-ray diffraction pattern of Cu Ka 1 radiation of wavelength λ of (theta)₂-θ₀)/(θ₀-θ₁) Greater than 0.54 and less than or equal to 1.0, wherein θ₀Is the angle corresponding to the maximum peak, and θ₁And theta₂Are respectively angles corresponding to the full width at half maximum, where θ₁<θ₂。

Technical Field

The present disclosure relates to a dielectric material and a multilayer ceramic electronic component using the same.

Background

In general, an electronic component using a ceramic material, such as a capacitor, an inductor, a piezoelectric element, a varistor, a thermistor, and the like, includes a ceramic body formed using the ceramic material, internal electrodes formed in the ceramic body, and external electrodes mounted on a surface of the ceramic body to be connected to the internal electrodes.

With the recent trend toward small-sized and multifunctional electronic components, chip components have tended to have smaller sizes and higher performance. Therefore, the multilayer ceramic capacitor is required to have a higher capacitance while having a smaller size.

For example, stacking a larger number of thinned dielectric layers and electrode layers in a multilayer ceramic capacitor is used as a method for achieving a smaller size and higher capacitance of the multilayer ceramic capacitor. Current dielectric layers all have a thickness of about 0.7 μm, and thin dielectric layers are being developed.

The miniaturization of the multilayer ceramic capacitor results in deterioration of product reliability, high-temperature withstand voltage characteristics, and DC bias characteristics. The term "DC bias characteristic" refers to the phenomenon in which the capacitance or dielectric constant decreases with increasing size of the DC bias field applied to the product.

For example, as in an applicable example of a power management integrated circuit or the like, a product is generally used in a state where a DC bias is applied. Furthermore, there is an increasing need to achieve efficient dielectric constants or capacitances under the application of high DC bias fields.

Disclosure of Invention

It is an aspect of the present disclosure to provide a dielectric material and a multilayer ceramic electronic component having an improved DC bias field dielectric constant.

An aspect of the present disclosure is to provide a dielectric material and a multilayer ceramic electronic component having improved high-temperature withstand voltage characteristics.

An aspect of the present disclosure is to provide a dielectric material and a multilayer ceramic electronic component capable of satisfying X5R.

According to an aspect of the present disclosure, a dielectric material includes: a main component of (Ba)_1-xCa_x)(Ti_1-yZr_y)O₃、(Ba_1-xCa_x)(Ti_1-ySn_y)O₃Or (Ba)_1-xCa_x)(Ti_1-yHf_y)O₃(0. ltoreq. x.ltoreq.1 and 0. ltoreq. y.ltoreq.0.05); and subcomponents. When Cu Ka 1 radiation (wavelength) is used) Among the peaks of the (002) and (200) planes of the X-ray diffraction (XRD) pattern of (A), the angle corresponding to the maximum peak is called theta₀And angles corresponding to a full width at half maximum (FWHM) are respectively referred to as θ₁And theta₂(θ₁<θ₂) When (theta)₂-θ₀)/(θ₀-θ₁) Greater than 0.54 and less than or equal to 1.0.

According to an aspect of the present disclosure, a multilayer ceramic electronic component includes: a ceramic body including a dielectric layer, a first internal electrode, and a second internal electrode; and first and second external electrodes respectively disposed on outer surfaces of the ceramic main body and respectively connected to the first and second internal electrodes. The dielectric layer comprises (Ba)_1-xCa_x)(Ti_{1- y}Zr_y)O₃、(Ba_1-xCa_x)(Ti_1-ySn_y)O₃Or (Ba)_1-xCa_x)(Ti_1-yHf_y)O₃(0. ltoreq. x.ltoreq.1 and 0. ltoreq. y.ltoreq.0.05). When Cu Ka 1 radiation (wavelength) is used) Among the peaks of the (002) and (200) planes of the XRD pattern of (A), the angle corresponding to the largest peak is called theta₀And angles corresponding to a full width at half maximum (FWHM) are respectively referred to as θ₁And theta₂(θ₁<θ₂) When (theta)₂-θ₀)/(θ₀-θ₁) Greater than 0.54 and less than or equal to 1.0.

According to an aspect of the present disclosure, a dielectric material includes: from (Ba)_1-xCa_x)(Ti_1-yZr_y)O₃、(Ba_1-xCa_x)(Ti_1-ySn_y)O₃Or (Ba)_1-xCa_x)(Ti_1-yHf_y)O₃Wherein x is 0. ltoreq. x.ltoreq.1 and y is 0. ltoreq. y.ltoreq.0.05; and subcomponents including a third subcomponent, a fourth subcomponent and a fifth subcomponent. The third subcomponent includes a compound of at least one element selected from elements including Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb. The fourth subcomponent includes a compound of at least one element selected from elements including Ba and Ca. The fifth subcomponent comprises at least one compound selected from the group consisting of: oxides of the element Si, carbonates of the element Si, and glasses containing the element Si. When the X-axis represents the number of moles of the fifth subcomponent and the Y-axis represents the sum of the number of moles of the third subcomponent and the fourth subcomponent based on 100 mole parts of the main component, the relationship among the number of moles of the third subcomponent, the fourth subcomponent and the fifth subcomponent belongs to the boundary or inside of the quadrangle shape of the connection point a (0.500, 1.900), the point B (0.500, 3.10), the point C (5.000, 5.400) and the point D (5.000, 3.900).

Drawings

The above and other aspects, features and advantages of the present disclosure will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings.

Fig. 1 is a schematic illustration of a microstructure after sintering according to an embodiment of the present disclosure.

Fig. 2 is a sectional view taken along line I-I' in fig. 1.

Fig. 3 is an enlarged view of the region "a" in fig. 2.

Fig. 4-6 are Scanning Electron Microscope (SEM) analysis images of prototype samples of the disclosed invention.

Figure 7 shows XRD analysis results of prototype samples of the disclosed invention.

Fig. 8 is a graph showing the dielectric constant according to the DC bias field of a prototype sample of the invention of the present disclosure.

Fig. 9 is a graph showing the dielectric constant of prototype samples of the invention of the present disclosure as a function of DC bias field at various temperatures.

Fig. 10 is a graph showing the contents of the third subcomponent, the fourth subcomponent and the fifth subcomponent of the experimental example of the invention of the present disclosure.

Detailed Description

Hereinafter, embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. This disclosure may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein but should be construed to include various modifications, equivalents, and/or alternatives to the embodiments of the disclosure. Similar reference numerals may be used for similar components as described with respect to the figures.

In the description, irrelevant descriptions will be omitted to clearly describe the present disclosure. In the drawings, the thickness may be exaggerated to clearly illustrate the various layers and regions. The same elements having the same function within the scope of the same concept will be described using the same reference numerals. Throughout the specification, unless specifically stated otherwise, when an element is referred to as "comprising" or "includes" one or more other elements, it is meant that it may also include, but not exclude, additional elements.

In this specification, expressions such as "having", "may have", "include" or "may include the presence of corresponding features (e.g., elements such as numbers, functions, operations, components, etc.) without excluding the presence of additional features.

In this specification, expressions such as "a or B", "at least one of a or/and B", "one or more of a or/and B", and the like may include all possible combinations listed together. For example, "a or B", "at least one of a and B", or "at least one of a or B" may refer to cases including: (1) at least one a, (2) at least one B, or (3) includes both at least one a and at least one B.

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

The present disclosure relates to a dielectric material, and a dielectric material according to the present disclosure is applied to an electronic component. Electronic components including the dielectric material of the present disclosure may include, for example, a capacitor, an inductor, a piezoelectric element, a varistor, or a thermistor, but the present disclosure is not limited thereto.

The dielectric material according to the embodiment may include (Ba)_1-xCa_x)(Ti_1-yZr_y)O₃、(Ba_1-xCa_x)(Ti_1-ySn_y)O₃Or (Ba)_1-xCa_x)(Ti_1-yHf_y)O₃(0. ltoreq. x.ltoreq.1 and 0. ltoreq. y.ltoreq.0.05). In the use of Cu Ka 1 radiation (wavelength)) Among the peaks of the (002) and (200) planes of the X-ray diffraction (XRD) pattern of (A), when the angle corresponding to the maximum peak is referred to as theta₀And angles corresponding to a full width at half maximum (FWHM) are respectively referred to as θ₁And theta₂(θ₁<θ₂) When (theta)₂-θ₀)/(θ₀-θ₁) Can be greater than 0.54 and less than or equal to 1.0.

In an example, the dielectric material of the present disclosure may include grains and grain boundaries. Fig. 1-3 are schematic diagrams illustrating a microstructure of a dielectric material according to an embodiment of the present disclosure. The dielectric material according to the present disclosure may be formed by sintering a main component and a sub-component, which will be described later. In addition, the dielectric material formed by sintering the main component and the sub-component may contain crystal grains 141 and grain boundaries 142.

In general, a dielectric material is required to have a characteristic of high dielectric constant. Therefore, improvement of crystallinity of a dielectric composition constituting a dielectric material has been studied. On the other hand, the present inventors found that the high DC bias field dielectric constant varies depending on the tetragonality (c/a) of crystal grains generated after sintering.

Three types of prototype multilayer ceramic capacitor (MLCC) samples were prepared and tested to confirm the relationship between the squareness (c/a) of the grains and the high DC bias field dielectric constant. FIGS. 4 to 6 show coarse-grained BaTiO particles₃(C-G), fine-grained BaTiO₃(F-G) and fine-grain Ba (Ba-doped) BaTiO₃The microstructure of (F-G-Ba), "doped Ba" refers to the case where the added Ba content is twice that of the other samples. The average sizes of the crystal grains confirmed by fig. 4 to 6 were 1740nm, 251nm, and 259nm, respectively. Therefore, the comparison between fig. 4(C-G) and fig. 5(F-G) reflects the difference in terms of the grain size, and the comparison between fig. 5(F-G) and fig. 6(F-G-Ba) shows the comparison result when the components are changed under the condition of the same particle diameter.

FIG. 7 shows the use of Cu Ka 1 radiation (wavelength)) BaTiO of (5)₃(002) And XRD patterns of (200) plane and (002) and (200) plane respectively corresponding to the powder type samples prepared by pulverizing C-G, F-G and F-G-Ba. As can be seen from fig. 7, the dimensions of the squareness (c/a) are as follows: C-G>F-G>F-G-Ba, and C-G show BaTiO₃(002) The clear peaks between the face and the (200) face are separated, but the two peaks partially overlap each other in F-G, and the two peaks completely overlap each other and have a substantially cubic structure in F-G-Ba.

Referring to FIG. 7, for C-G, F-G and F-G-Ba, Cu Ka 1 radiation (wavelength) is used) Among the peaks of the (002) and (200) planes of the XRD pattern of (1), when the angle corresponding to the maximum peak is referred to as theta₀And angles corresponding to full width at half maximum (FWHM) are respectively setReferred to as θ₁And theta₂(θ₁<θ₂) When (theta)₀-θ₁) May refer to the difference "a" between the angle corresponding to the maximum peak and the angle corresponding to the smaller angle of FWHM (θ)₂-θ₀) May refer to the difference "B" between the angle corresponding to the larger angle of the FWHM and the angle corresponding to the maximum peak. In this case, it was confirmed that the value of B/A decreased as the squareness (C/a) increased to 1.004(F-G-Ba), 1.007(F-G) and 1.009 (C-G).

FIG. 8 shows the dielectric constant of the DC bias field according to C-G, F-G and F-G-Ba at room temperature. It can be seen from fig. 8 that the dielectric constant in the high DC bias field of greater than or equal to 8V/μm increases as the grain size decreases from C-G to F-G. In addition, when F-G and F-G-Ba are compared under the condition of the same crystal grain size, it is confirmed that the dielectric constant in a high DC bias field of 8V/μm or more increases depending on the composition of the dielectric material. Such results indicate that the high DC bias field dielectric constant can be improved by varying the composition of the dielectric material.

From the above results, it was confirmed that as the squareness of the dielectric material decreases, B/a (the ratio of the difference between the angle corresponding to the larger angle of the FWHM and the angle corresponding to the maximum peak to the difference between the angle corresponding to the maximum peak and the angle corresponding to the smaller angle of the FWHM) increases and the high DC bias field dielectric constant improves. In addition, it was confirmed that Cu K.alpha.1 radiation (wavelength) was used) Among the peaks of the (002) and (200) planes of the XRD pattern of (1), when the angle corresponding to the maximum peak is referred to as theta₀And angles corresponding to a full width at half maximum (FWHM) are respectively referred to as θ₁And theta₂(θ₁<θ₂) And (theta)₂-θ₀)/(θ₀-θ₁) (B/A ═ ratio of the difference between the angle corresponding to the larger angle of FWHM and the angle corresponding to the maximum peak to the difference between the angle corresponding to the maximum peak and the angle corresponding to the smaller angle of FWHM) greater than 0.54, the dielectric material has an improved high DC bias field dielectricA constant.

Ratio of difference between angles (θ)₂-θ₀)/(θ₀-θ₁) (═ B/a) can be greater than 0.54, greater than or equal to 0.55, greater than or equal to 0.56, greater than or equal to 0.57, or greater than or equal to 0.58, and less than or equal to 1 or less than 1, although the disclosure is not so limited. Ratio of difference between angles (theta)₂-θ₀)/(θ₀-θ₁) When (═ B/a) satisfies the above range, the dielectric material has an improved high DC bias field dielectric constant.

The dielectric material according to the embodiment may include a main component and a sub-component, and the sub-component may include at least one of the first sub-component to the sixth sub-component. In the present specification, the term "main component" may refer to a component in a relatively higher weight ratio than other components, and may refer to a component contained in an amount of greater than or equal to 50 wt% based on the total weight of the composition or the dielectric material layer. In addition, the term "subcomponent" may refer to an ingredient that accounts for a relatively lower weight ratio than the main ingredient, and may refer to an ingredient that is contained in an amount of less than 50 wt% based on the total weight of the composition or the dielectric material layer.

Hereinafter, each composition of the dielectric material according to the embodiment will be described in more detail.

Principal component

The dielectric material according to an embodiment may comprise (Ba)_1-xCa_x)(Ti_1-yZr_y)O₃、(Ba_1-xCa_x)(Ti_1-ySn_y)O₃Or (Ba)_1-xCa_x)(Ti_1-yHf_y)O₃(0. ltoreq. x.ltoreq.1, 0. ltoreq. y.ltoreq.0.05). The main component may be, for example, one in which a part of Ca, Zr, Sn and/or Hf is dissolved in BaTiO in solid solution₃The chemical compound of (1). In the composition formula, x may be in the range of greater than or equal to 0 and less than or equal to 1, and y may be in the range of greater than or equal to 0 and less than or equal to 0.05, but the disclosure is not limited thereto. For example, in the composition formula, when x is 0, y is 0, and z is 0, the main component may be BaTiO₃。

The first subcomponent

According to an embodiment, a dielectric material according to the present disclosure may comprise at least one variable valence acceptor element as a first subcomponent. In some embodiments, the dielectric material may include at least one selected from the group consisting of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn, their oxides, and their carbonates as the first subcomponent. In some embodiments, the variable valence acceptor element may comprise Mn, V, Cr, Fe, Ni, Co, Cu, or Zn.

The first subcomponent may be contained in an amount of greater than or equal to 0.1 molar part or less than or equal to 1.0 molar part based on 100 molar parts of the main component. The first subcomponent may be included in a range of greater than or equal to 0.1 molar part and less than or equal to 1.0 molar part based on 100 molar parts of the main component. The content of the first subcomponent may be a total content of Mn, V, Cr, Fe, Ni, Co, Cu, or Zn elements contained in the first subcomponent regardless of an added form (such as an oxide or carbonate form). For example, when V₂O₅When the (oxide of V) is contained in 0.1 molar parts, the sum of the contents of the elements V may be 0.2 molar parts.

The first subcomponent is used to improve the reduction resistance of the dielectric ceramic composition to improve the high-temperature withstand voltage characteristics of a multilayer ceramic electronic component to which the dielectric material is applied.

Second subcomponent

According to an embodiment, a dielectric material according to the present disclosure may include, as a second subcomponent, at least one of a fixed valence acceptor element including Mg, an oxide thereof, and a carbonate thereof.

The second subcomponent may be contained in an amount of less than or equal to 2.0 molar parts based on 100 molar parts of the main component. The content of the second subcomponent may be based on the content of the Mg element contained in the second subcomponent regardless of the form of the element (such as the form of an oxide or a carbonate). The lower limit of the second subcomponent need not be limited. However, the lower limit of the second subcomponent may be, for example, greater than or equal to 0 molar part or greater than 0 molar part based on 100 molar parts of the main component, but is not limited thereto.

When the content of the second sub-component is more than 2.0 parts by mole based on 100 parts by mole of the main component, the dielectric constant may decrease and the high-temperature withstand voltage characteristic may deteriorate.

The third subcomponent

According to an embodiment, the dielectric material according to the present disclosure may include, as a third sub-component, at least one selected from the group consisting of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, Yb, oxides thereof, and carbonates thereof.

The third subcomponent may be contained in an amount of greater than or equal to 0.3 molar parts or less than or equal to 5.4 molar parts based on 100 molar parts of the main component. The third subcomponent may be included in a range of greater than or equal to 0.3 molar parts and less than or equal to 5.4 molar parts based on 100 molar parts of the main component. The content of the third subcomponent may be the total content of elements among Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb contained in the third subcomponent regardless of the form of addition (such as the form of oxide or carbonate).

The third sub-component may be used to prevent deterioration in reliability of the multilayer ceramic electronic component to which the dielectric material according to the example is applied. When the third subcomponent is outside the above range, high temperature withstand voltage characteristics may be deteriorated.

The fourth subcomponent

According to an embodiment, a dielectric material according to the present disclosure may include a fourth subcomponent including one or more of Ba and Ca, their oxides, and their carbonates.

The fourth subcomponent may be contained in an amount of 5.0 molar parts or less based on 100 molar parts of the main component. The lower limit of the fourth subcomponent may be, for example, 0 or more molar parts or 0 or more molar parts based on 100 molar parts of the main component. The content of the fourth subcomponent may be a total content of Ba and Ca contained in the fourth subcomponent regardless of an added form (such as a form of an oxide or a carbonate).

The fourth subcomponent may be included in an amount of 5.0 molar parts based on 100 molar parts of the main component to adjust the crystal structure of the dielectric material according to the present disclosure.

The fifth subcomponent

According to an embodiment, the dielectric material according to the present disclosure may include a fifth subcomponent including at least one selected from the group consisting of an oxide of an Si element, a carbonate of an Si element, and a glass including an Si element.

The fifth subcomponent may be contained in an amount of greater than or equal to 0.5 molar parts or less than or equal to 5.0 molar parts based on 100 molar parts of the main component. The fifth subcomponent may be included in a range of greater than or equal to 0.5 molar parts and less than or equal to 5.0 molar parts based on 100 molar parts of the main component. The content of the fifth subcomponent may be based on the content of the Si element contained in the fifth subcomponent regardless of the form of the Si element (such as the form of an oxide or a carbonate).

When the content of the fifth subcomponent is less than 0.5 parts by mole based on 100 parts by mole of the main component, the dielectric constant and the high temperature withstand voltage may be reduced. When the content of the fifth subcomponent is more than 5.0 parts by mole, problems such as a reduction in sinterability and denseness, secondary formation, and the like may occur.

The sixth subcomponent

According to an embodiment, the dielectric material according to the present disclosure may include a sixth subcomponent including at least one selected from the group consisting of Na, Li, an oxide thereof, and a carbonate thereof.

The sixth subcomponent may be contained in an amount of less than or equal to 1.0 molar part based on 100 molar parts of the main component. The lower limit of the content of the sixth subcomponent may be, for example, greater than or equal to 0 molar part or greater than 0 molar part based on 100 molar parts of the main component.

The content of the sixth subcomponent may be based on the total content of Na and Li elements contained in the sixth subcomponent regardless of the added form (such as the form of an oxide or a carbonate). The sixth subcomponent may be included as a sintering aid and may be used to reduce the sintering temperature.

In an example, a dielectric ceramic composition according to the present disclosure may include the above-described third subcomponent, fourth subcomponent, and fifth subcomponent. When the X-axis represents the molar part of the fifth subcomponent and the Y-axis represents the sum of the molar parts of the third subcomponent ("RE" in fig. 10) and the fourth subcomponent based on 100 molar parts of the main component, the relationship among the molar parts of the third subcomponent, the fourth subcomponent and the fifth subcomponent may belong to the boundary or the inside of the quadrangle connecting point a (0.500, 1.900), point B (0.500, 3.10), point C (5.000, 5.400) and point D (5.000, 3.900).

Fig. 10 shows the boundary and the inside of a quadrangle connecting point a, point B, point C, and point D. The boundary and the inside of the quadrangle connecting the point a, the point B, the point C, and the point D can be confirmed by an embodiment which will be described later.

The present disclosure also relates to a multilayer ceramic electronic component.

Fig. 1 is a schematic perspective view of a multilayer ceramic electronic component according to an embodiment, fig. 2 is a sectional view of the multilayer ceramic electronic component taken along line I-I' in fig. 1, and fig. 3 is an enlarged view of region "a" in fig. 2.

Referring to fig. 1 to 3, a multilayer ceramic electronic component 100 according to an embodiment may include a ceramic main body 110, the ceramic main body 110 including a dielectric layer 111, a first internal electrode 121, and a second internal electrode 122. The multilayer ceramic electronic component 100 may include first and second external electrodes 131 and 132, the first and second external electrodes 131 and 132 being disposed on the outer surface of the ceramic body 110 and connected to the first and second internal electrodes 121 and 122, respectively.

The shape of the ceramic main body 110 is not necessarily limited, but may be a hexahedral shape or a shape similar to a hexahedral shape, as shown in the drawings. Even in the case where the ceramic main body 110 does not have a perfectly rectilinear hexahedral shape due to shrinkage of ceramic powder particles contained in the ceramic main body 110 in the sintering process, the ceramic main body 110 may have a substantially hexahedral shape.

The ceramic main body 110 may be formed by alternately laminating ceramic green sheets on which the first internal electrodes 121 are printed and ceramic green sheets on which the second internal electrodes 122 are printed in a thickness direction (Z direction).

In the ceramic main body 110, the dielectric layers 111 and the internal electrodes 121 and 122 may be alternately laminated along the third direction. The plurality of dielectric layers 111 constituting the ceramic main body 110 may be in a sintered state, and adjacent dielectric layers 111 may be integrated with each other such that a boundary between them is not apparent without using a Scanning Electron Microscope (SEM).

According to an embodiment, the dielectric layer 111 may include the above-mentioned dielectric material having a layered structure, and may include (Ba)_1-xCa_x)(Ti_1-yZr_y)O₃、(Ba_1-xCa_x)(Ti_1-ySn_y)O₃Or (Ba)_1-xCa_x)(Ti_1-yHf_y)O₃(0. ltoreq. x.ltoreq.1 and 0. ltoreq. y.ltoreq.0.05). In addition to the main component and the sub-component of the above dielectric material, various ceramic additives, organic solvents, plasticizers, binders, dispersants, and the like may be added as the material of the dielectric layer 111 according to the purpose of the present disclosure.

The dielectric layer 111 is formed by adding additives required for slurry (containing the above-described main component and sub-component), and coating the slurry onto a carrier film and drying on the carrier film to prepare a plurality of ceramic sheets. Each of the ceramic sheets may be prepared by forming the slurry into a sheet having a thickness of several micrometers (μm) using a doctor blade method, but the present disclosure is not limited thereto.

In the dielectric layer 111, when Cu Ka 1 radiation (wavelength) is used) Among the peaks of the (002) and (200) planes of the XRD pattern of (A), the angle corresponding to the largest peak is called theta₀And angles corresponding to a full width at half maximum (FWHM) are respectively referred to as θ₁And theta₂(θ₁<θ₂) When (theta)₂-θ₀)/(θ₀-θ₁) Can be greater than 0.54 and less than or equal to 1.0. Since the contents related to the XRD pattern are the same as those described above, detailed description thereof will be omitted。

The first and second internal electrodes 121 and 122 may be stacked such that end surfaces thereof are alternately exposed to surfaces of both end portions of the ceramic main body 110 opposite to each other, respectively. The materials of the first and second internal electrodes 121 and 122 are not necessarily limited. For example, the first and second internal electrodes 121 and 122 may be formed using a conductive paste including at least one of silver (Ag), palladium (Pd), gold (Au), platinum (Pt), nickel (Ni), copper (Cu), tin (Sn), tungsten (W), titanium (Ti), and an alloy thereof. The printing method of the conductive paste may be a screen printing method, a gravure printing method, etc., but is not limited thereto.

In the multilayer ceramic electronic component according to the example of the disclosed invention, the first and second external electrodes 131 and 132 may be disposed on the outer surface of the ceramic body. The first external electrode 131 may be connected to the first internal electrode 121, and the second external electrode 132 may be connected to the second internal electrode 122.

The first and second external electrodes 131 and 132 may include a conductive metal. The conductive metal may be at least one of 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.

In another example of the disclosed invention, the subcomponents of the multilayer ceramic electronic component according to the present disclosure may include at least one of the following subcomponents: a first subcomponent including at least one compound selected from the group consisting of variable valence acceptor elements (including one or more elements among Mn, V, Cr, Fe, Ni, Co, Cu, and Zn), oxides thereof, and carbonates thereof; a second subcomponent including at least one compound selected from the group consisting of fixed valence acceptor elements including Mg, oxides thereof, and carbonates thereof; a third subcomponent including at least one compound selected from the group consisting of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb, oxides thereof, and carbonates thereof; a fourth subcomponent including at least one compound selected from the group consisting of Ba and Ca, their oxides, and their carbonates; a fifth subcomponent including at least one compound selected from the group consisting of an oxide of an element Si, a carbonate of an element Si, and a glass containing an element Si; and a sixth subcomponent including at least one compound selected from the group consisting of a compound containing a Na element, a compound containing a Li element, an oxide thereof, and a carbonate thereof.

In another example of the disclosed invention, the subcomponents of the multilayer ceramic electronic component may comprise: a third subcomponent including at least one compound selected from the group consisting of a compound including an element of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd or Yb, an oxide including an element of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd or Yb, and a carbonate including an element of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd or Yb; a fourth subcomponent including at least one compound selected from the group consisting of a compound containing an element Ba or Ca, an oxide containing an element Ba or Ca, and a carbonate containing an element Ba or Ca; and a fifth subcomponent including at least one compound selected from the group consisting of an oxide of an element Si, a carbonate of an element Si, and a glass containing an element Si. When the X-axis represents the molar part of the fifth subcomponent and the Y-axis represents the sum of the molar parts of the third subcomponent and the fourth subcomponent based on 100 molar parts of the main component, the relationship among the molar parts of the third subcomponent, the fourth subcomponent and the fifth subcomponent may belong to the boundary or the inside of a quadrangle connecting point a (0.500, 1.900), point B (0.500, 3.10), point C (5.000, 5.400) and point D (5.000, 3.900).

Detailed descriptions of the dielectric material, the main component, and the sub-component are the same as those of the above-described dielectric material according to the embodiment, and thus will be omitted. In this specification, although a description has been given of the case where the multilayer ceramic electronic component is a multilayer ceramic capacitor, the present disclosure is not limited thereto.

Hereinafter, although the present disclosure will be described in more detail with reference to examples disclosed for illustrative purposes, the present disclosure is not limited thereto.

Examples of the invention

In this example, Ba having an average particle diameter of 100nm is usedTiO₃The powder particles are used as the raw material of the main component. Raw material powder particles corresponding to the main component and the sub-component of compositions 1-1 to 5-3 listed in table 1 were ground for 10 hours by using zirconia balls as a mixing/dispersing medium and mixing ethanol/toluene with a dispersant. After the binder was mixed with the mixed solution, the raw material powder particles were further ground for 10 hours.

Examples 1-2-A, examples 1-2-B and examples 1-2-C listed in Table 1 represent the following examples: prior to the introduction of the binder, the milling time was increased to 15, 20, and 30 hours, respectively, to reduce the tetragonality (c/a) of the dielectric material (e.g., to increase the B/a of the XRD peaks).

The prepared slurry was used to manufacture molding sheets (molding sheet) having thicknesses of 0.8 μm and 10 μm, respectively, by a molding machine (molding machine) for manufacturing film sheets. Nickel (Ni) internal electrodes are printed on each of the molded sheets.

A top cover and a bottom cover were manufactured by laminating cover sheets (having a thickness of 10 to 13 μm) into 25 layers, and a press bar was manufactured by pressing and laminating 21 layers of the printed active sheet.

The press bar was cut into pieces having a size of 3.2mm × 1.6mm using a cutter. Fully fabricated MLCC sheets of 3216 size were plasticized and then at a temperature of about 1080 ℃ to 1120 ℃ at 0.1% H₂/99.9％N₂To 1.0% H₂/99.0％N₂(H₂O/H₂/N₂Atmosphere) for a sintering time in the range of 10 minutes to 1 hour. Sintering the MLCC chip in N₂Heat treatment was carried out at a temperature of about 950 c for 3 hours under an atmosphere to reoxidize.

The external electrode is completed by performing a capping process and an electrode sintering process on the sintered sheet using Cu paste. Thus, MLCC sheets having dimensions of 3.2mm × 1.6mm were produced after sintering (the dielectric material had a thickness of about 0.6 μm and the number of dielectric layers was 20).

The room temperature capacitance and dielectric loss of the MLCC sheet were measured using an LCR meter under conditions of 1kHz and AC 0.5V/μm. The dielectric constant of the dielectric material of the MLCC sheet is calculated from the capacitance and the thickness of the dielectric layer of the MLCC, the area of the internal electrode, and the number of laminated layers in the MLCC.

The room temperature insulation resistance IR was measured after 60 seconds in a state where a sample was taken at 10V and DC was applied at 10V/. mu.m.

The change in capacitance according to temperature was measured in a temperature range of-55 ℃ to 145 ℃.

The high temperature IR boost test measures resistance degradation behavior while increasing a voltage step at DC 10V/μm at 150 ℃, the resistance value is measured every 5 seconds, and the time of each step is 1 hour. The high temperature withstand voltage was obtained by the high temperature IR pressure rise test. The high temperature withstand voltage means that when a DC voltage level of 5V/. mu.m is applied to a 3216-sized chip comprising 20 dielectric layers after sintering, at a temperature of 150 ℃ for 1 hour, and then each step is increased continuously by 5V/. mu.m, IR is allowed to remain at 10 or more⁶Maximum voltage of Ω.

TABLE 1

Table 2 shows the properties of the prototype sheet corresponding to the examples listed in table 1.

TABLE 2

Referring to tables 2 and 4, characterization measurements are shown. In tables 2 and 4, "O" represents a case where all the conditions (high DC bias field dielectric constant @8V/μm (dielectric constant when DC 8V/μm is applied) of 1000 or more, high temperature (150 ℃ C.) withstand voltage of 50V/μm or more, and absolute value of Temperature Coefficient of Capacitance (TCC) (85 ℃ C.) of less than 15%) are satisfied, and "X" represents a case where any of the above conditions is not satisfied.

In table 1, examples 1-1 to 1-4 show the content change of the fourth subcomponent Ba or Ca under the fixing conditions: based on 100 molesBaTiO raw material having a size of 80nm as a main component of (A)₃The first subcomponent has a total of 0.3mol of Mn and V as variable valence elements, the second subcomponent Mg has a content of 0mol, the third subcomponent has a content of 0.3mol of Dy as rare earth element, the fifth subcomponent Si has a content of 0.5mol, and the sixth subcomponent has a total of 0.4mol of Na and Li. Table 2 shows the properties of prototype MLCC samples corresponding to examples 1-1 to examples 1-4.

When the content of Ba was 1.2mol (example 1-1), the B/A of the XRD peak of (002)/(200) plane was 0.50 and the high DC bias field dielectric constant was less than 1000. When the content of Ba was increased to 2.0mol (examples 1-2), the B/A of the XRD peak was increased to 0.58, and all the aimed characteristics of the present disclosure, such as a high DC bias field dielectric constant @8V/μm (dielectric constant when DC 8V/μm is applied) of 1000 or more, a high temperature (150 ℃ C.) withstand voltage of 50V/μm or more, and an absolute value of TCC (85 ℃ C.) of less than 15%, were satisfied. Even when Ba was replaced with Ca having the same content (examples 1-3), substantially the same characteristics as in example 1-2 were obtained. When the content of Ba was further increased to 2.8mol (examples 1 to 4), B/A was further increased to 0.92, and the high DC bias field dielectric constant @ 8V/. mu.m was also further increased to 1115.

In table 1, examples 2-1 to 2-3 show the content change of the fourth subcomponent Ba under the fixed conditions: BaTiO raw material having a size of 80nm based on 100 moles of main component₃The first subcomponent has a total of 0.3mol of Mn and V as variable valence elements, the second subcomponent Mg has a content of 0.2mol, the third subcomponent has a content of 0.3mol of Dy as rare earth element, the fifth subcomponent Si has a content of 1.25mol, and the sixth subcomponent has a total of 1.0mol of Na and Li. Table 2 shows the properties of prototype MLCC samples corresponding to examples 2-1 to 2-3.

When the content of Ba was 1.6mol (example 2-1), the B/A of the XRD peak of (002)/(200) plane was 0.51 and the high DC bias field dielectric constant was less than 1000. When the content of Ba was increased to 2.4mol (example 2-2), B/A of XRD peak was increased to 0.63, and all the aimed characteristics of the present disclosure, such as high DC bias field dielectric constant @8V/μm (dielectric constant when DC 8V/μm is applied) of 1000 or more, high temperature (150 ℃ C.) withstand voltage of 50V/μm or more, and absolute value of TCC (85 ℃ C.) of less than 15%, were satisfied. When the content of Ba was further increased to 3.2mol (examples 2-3), B/A was further increased to 0.82, and the high DC bias field dielectric constant @ 8V/. mu.m was also further increased to 1102.

In table 1, examples 3-1 to 3-3 show the content change of the fourth subcomponent Ba under the fixed conditions: BaTiO raw material having a size of 80nm based on 100 moles of main component₃The first subcomponent has a total of 0.3mol of Mn and V as variable valence elements, the second subcomponent Mg has a content of 0.2mol, the third subcomponent has a content of 1.4mol of Dy as rare earth element, the fifth subcomponent Si has a content of 2.75mol, and the sixth subcomponent has a total of 0.4mol of Na and Li. Table 2 shows the properties of prototype MLCC samples corresponding to examples 3-1 to 3-3.

When the content of Ba was 1.2mol (example 3-1), the B/A of the XRD peak of (002)/(200) plane was 0.48 and the high DC bias field dielectric constant was less than 1000. When the content of Ba was increased to 2.0mol (example 3-2), B/A of XRD peak was increased to 0.66, and all the aimed characteristics of the present disclosure, such as high DC bias field dielectric constant @8V/μm (dielectric constant when DC 8V/μm is applied) of 1000 or more, high temperature (150 ℃ C.) withstand voltage of 50V/μm or more, and absolute value of TCC (85 ℃ C.) of less than 15%, were satisfied. When the content of Ba was further increased to 2.8mol, B/A was further increased to 0.94, and the high DC bias field dielectric constant @ 8V/. mu.m was also further increased to 1123.

In table 1, examples 4-1 to 4-4 show the content change of the fourth subcomponent Ba under the fixed conditions: BaTiO raw material having a size of 80nm based on 100 moles of main component₃The sum of Mn and V as variable valence elements in the first subcomponent is 0.3mol, the content of Mg as the second subcomponent is 2.0mol, the content of Dy as a rare earth element in the third subcomponent is 1.0mol, and the content of Si as the fifth subcomponent is 3.38 mol. Table 2 shows the properties of prototype MLCC samples corresponding to examples 4-1 to 4-4.

When the content of Ba was 1.85mol (example 4-1), the B/A of the XRD peak of (002)/(200) plane was 0.48 and the high DC bias field dielectric constant was less than 1000. When the content of Ba was increased to 2.7mol (example 4-2), the B/A of the XRD peak was increased to 0.60, and all the aimed characteristics of the present disclosure, such as a high DC bias field dielectric constant @8V/μm (dielectric constant when DC 8V/μm is applied) of 1000 or more, a high temperature (150 ℃ C.) withstand voltage of 50V/μm or more, and an absolute value of TCC (85 ℃ C.) of less than 15%, were satisfied. Even when Ba was replaced with Ca having the same content (example 4-3), substantially the same characteristics as in example 4-2 were obtained. When the content of Ba was further increased to 3.65mol, B/A was further increased to 0.92, and the high DC bias field dielectric constant @ 8V/. mu.m was also further increased to 1133.

In table 1, examples 5-1 to 5-3 show the content change of the fourth subcomponent Ba under the fixed conditions: BaTiO raw material having a size of 80nm based on 100 moles of main component₃The sum of Mn and V as variable valence elements in the first subcomponent is 1.0mol, the content of Mg as the second subcomponent is 1.0mol, the content of Dy as a rare earth element in the third subcomponent is 1.0mol, and the content of Si as the fifth subcomponent is 5.00 mol. Table 2 shows the properties of prototype MLCC samples corresponding to examples 5-1 to 5-3.

When the content of Ba was 2.4mol (example 5-1), the B/A of the XRD peak of (002)/(200) plane was 0.52 and the high DC bias field dielectric constant was less than 1000. When the content of Ba was increased to 3.4mol (example 5-2), B/A of XRD peak was increased to 0.61, and all the aimed characteristics of the present disclosure, such as high DC bias field dielectric constant @8V/μm (dielectric constant when DC 8V/μm is applied) of 1000 or more, high temperature (150 ℃ C.) withstand voltage of 50V/μm or more, and absolute value of TCC (85 ℃ C.) of less than 15%, were satisfied. When the content of Ba was further increased to 4.4mol, B/A was further increased to 0.85, and the high DC bias field dielectric constant @ 8V/. mu.m was also further increased to 1098.

In Table 1, examples 1-2-A to 1-2-C are BaTiO raw materials having a size of 80nm when the subcomponents corresponding to examples 1-2 were applied to 100 moles of the main component₃Examples according to the mixing and milling time of the batch slurry. Table 2 shows the properties of prototype MLCC samples corresponding to examples 1-2-A through 1-2-C.

The mixing and grinding times for examples 1-2, 1-2-A, 1-2-B and 1-2-C were 10, 15, 20 and 30 hours, respectively. As the hybrid milling time was increased to 10, 15 and 20 hours, the high DC bias field dielectric constant @8V/μm increased to 1018, 1084 and 1103 while increasing the B/A of the (002)/(200) plane XRD peaks to 0.58, 0.70 and 0.85. Therefore, even when the squareness (c/a) of the dielectric material is reduced and the B/A of the XRD peak is increased by increasing the mixed milling time, not by adjusting the components of the subcomponent additives, the high DC bias field dielectric constant @8V/μm is improved. On the other hand, when the hybrid milling time was excessively increased to 30 hours (example of 1-2-C), the grain size of the dielectric material rapidly increased, so that the B/A of the XRD peak was decreased to rapidly decrease the high DC bias field dielectric constant @8V/μm to 726.

TABLE 3

TABLE 4

In table 3, examples 6 to 14 applied subcomponents corresponding to examples 1-2, and were examples varying in composition according to the raw material having a size of 100nm of the main component. Table 4 shows the properties of prototype MLCC samples of examples 6 to 14.

When a portion of Ti was replaced by Zr, as the Zr content increased from 0 to 0.020 and 0.050 (examples 1-2, 6 and 7), the B/A of the (002)/(200) plane XRD peaks increased from 0.58 to 0.71 and 0.84, and the high DC bias field dielectric constant @ 8V/. mu.m increased from 1018 to 1117 and 1205, while the 85 ℃ TCC decreased from-11.8% to-12.6% and-14.7%. Therefore, it was confirmed that the high DC bias field dielectric constant @8V/μm was improved even when the B/A of the XRD peak of the (002)/(200) plane was increased by substituting a part of the Ti element with Zr, not by adjusting the composition of the subcomponent additives. On the other hand, when ZrWhen the content was excessively increased from 0 to 0.070 (example 8), the B/A of the XRD peak was further increased and the high DC bias field dielectric constant @8V/um was further increased to 1284, but TCC was also reduced to-18.4% at 85 ℃, resulting in unsatisfactory TCC characteristics. Thus, in the formula Ba (Ti)_1-yZr_y)O₃In the range of 0 to 0.05, the content of Zr in the components of the main component satisfies the objective characteristics of the present disclosure.

In table 3, examples 9 to 11 and examples 12 to 14 are those in which a part of Ti as a main component is substituted by Sn and Hf and their contents are in the formula Ba (Ti)_1-ySn_y)O₃(examples 9 to 11) and Ba (Ti)_1-yHf_y)O₃Examples of (examples 12 to 14) increased to 0.020, 0.050, and 0.070. Table 4 shows the properties of prototype MLCC samples corresponding to examples 9-11 and 12-14.

Similar to the case where Zr was substituted, as the Sn and Hf contents were increased to 0.020 and 0.050 (example 9, example 10, example 12 and example 13), the 85 ℃ TCC was decreased to the range satisfying the specification, the B/A of the (002)/(200) plane XRD peak was increased, and the high DC bias field dielectric constant @8V/μm was increased. On the other hand, when the contents of Sn and Hf are excessively increased to 0.070 (examples 11 and 14), B/A of XRD peak is further increased and high DC bias field dielectric constant @8V/μm is also further increased, but 85 ℃ TCC does not satisfy X5R TCC characteristic (required to be in the range of. + -. 15%). Therefore, when in formula Ba (T)_1-ySn_y)O₃And Ba (T)_1-yHf_y)O₃The content of Zr or Sn or Hf in the component of the main component is in the range of 0 to 0.05, the target characteristics of the present disclosure are satisfied.

In addition, the boundary value of the sum of the contents of the third subcomponent and the fourth subcomponent based on the content of the fifth subcomponent shown in FIG. 10 can be confirmed by examples 1 to 4, examples 2 to 3, examples 3 to 3, examples 4 to 4, and examples 5 to 3. Further, it was confirmed that example 1-2, example 2-2, example 3-2, example 4-2 and example 5-2 satisfied the characteristic measurement, whereas example 1-1, example 2-1, example 3-1, example 4-1 and example 5-1 did not satisfy the characteristic measurement. Since it was confirmed that the characteristic measurement was changed at the intermediate values of example 1-1, example 2-1, example 3-1, example 4-1 and example 5-1 and example 1-2, example 2-2, example 3-2, example 4-2 and example 5-2, the intermediate values of the above examples were determined as boundary values. As a result, it was confirmed that when the content ranges of the third subcomponent, the fourth subcomponent and the fifth subcomponent fall within the boundary or inside of the quadrangle connecting A, B, C and D of fig. 10, improved high temperature withstand voltage and high DC bias field characteristics can be exhibited.

As described above, according to the present disclosure, a dielectric material and a multilayer ceramic electronic component having an improved DC bias field dielectric constant can be provided.

In addition, a dielectric material and a multilayer ceramic electronic component having improved high-temperature withstand voltage characteristics can be provided.

Further, a dielectric material and a multilayer ceramic electronic component capable of satisfying X5R can be provided.

While embodiments have been shown and described above, it will be apparent to those skilled in the art that modifications and variations can be made without departing from the scope of the disclosure as defined by the appended claims.