Dielectric and multilayer ceramic electronic component containing the same

Abstract

To provide a dielectric substance and a laminated ceramic electronic component having excellent dc bias permittivity.SOLUTION: One embodiment of the present invention provides a dielectric substance involving a main component represented by (Ba1-xCax)(Ti1-y(Zr, Sn, Hf)y)O3 (0≤x≤1, 0≤y≤0.05) and accessory components; when an angle corresponding to the maximum peak in XRD pattern peaks of (002) and (200) planes using Cu Kα1 radiation (wavelength λ=1.5406Å) is shown as θ0 and angles corresponding to a half band width (FWHM, Full Width at Half Maximum) are shown as θ1 and θ2, respectively (θ1<θ2), (θ2-θ0) / (θ0-θ1) is over 0.54 and 1.0 or under.SELECTED DRAWING: Figure 3

Description

[Technical Field]

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

[0002] In general, electronic components using ceramic materials, such as capacitors, inductors, piezoelectric elements, varistors, or thermistors, include a ceramic body made of a ceramic material, internal electrodes formed inside the body, and external electrodes disposed on the surface of the ceramic body so as to be connected to the internal electrodes.

[0003] Recently, as electronic products become smaller and more multifunctional, chip components also tend to become smaller and more functional. This has led to a demand for multilayer ceramic capacitors that are small in size and have a large capacitance.

[0004] For example, one way to achieve both miniaturization and high capacitance in multilayer ceramic capacitors is to stack a large number of internal dielectric and electrode layers by reducing their thickness. However, the current thickness of the dielectric layer is around 0.7 μm, and development is continuing to move toward thinner layers.

[0005] As mentioned above, the miniaturization of multilayer ceramic capacitors has led to problems with product reliability, high-temperature voltage resistance, and a decline in dc-bias characteristics. The dc-bias characteristics refer to the phenomenon in which capacitance and dielectric constant decrease as the size of the dc-bias field applied to a product increases.

[0006] For example, in applications such as power management integrated circuits, products are often used with a dc bias applied, and there is an increasing demand for properties that achieve a high effective dielectric constant and capacitance under conditions where a high electric field dc bias is applied. Summary of the Invention [Problem to be solved by the invention]

[0007] One of the various objects of the present invention is to provide a dielectric and a multilayer ceramic electronic component having an excellent dc bias dielectric constant.

[0008] One of the various objects of the present invention is to provide a dielectric and a multilayer ceramic electronic component having excellent high-temperature voltage resistance characteristics.

[0009] One of the various objects of the present invention is to provide dielectric and multilayer ceramic electronic components that can meet X5R or X7R. [Means for solving the problem]

[0010] One embodiment of the present invention is 1-x Ca x )(Ti 1-y (Zr, Sn, Hf) y )O3 (where 0≦x≦1, 0≦y≦0.05), and the ratio (θ2−θ0) / (θ0−θ1) is greater than 0.54 and not greater than 1.0, where θ0 is the angle corresponding to the maximum peak in the XRD pattern of the (002) and (200) planes obtained using Cu Kα1 radiation (wavelength λ1.5406 Å), and θ1 and θ2 are the angles corresponding to the full width at half maximum (FWHM), respectively (where θ1<θ2).

[0011] Another embodiment of the present invention is a ceramic body including a dielectric layer, a first internal electrode, and a second internal electrode; and a first external electrode and a second external electrode disposed on an outer surface of the ceramic body and connected to the first internal electrode and the second internal electrode, respectively, wherein the dielectric layer is (Ba 1-x Ca x )(Ti 1-y (Zr, Sn, Hf) y)O3 (where 0≦x≦1, 0≦y≦0.05), and a subcomponent, wherein, in the peaks of the XRD pattern of the (002) and (200) planes using Cu Kα1 radiation (wavelength λ1.5406 Å), the angle corresponding to the maximum peak is θ0, and the angles corresponding to the full width at half maximum (FWHM) are θ1 and θ2, respectively (where θ1<θ2), and (θ2-θ0) / (θ0-θ1) is greater than 0.54 and less than or equal to 1.0. [Effects of the Invention]

[0012] One of the various advantages of the embodiments of the present invention is that it can provide a dielectric and a multilayer ceramic electronic component with an increased high electric field dc bias dielectric constant.

[0013] One of the various advantages of the embodiments of the present invention is that it can provide a dielectric and a multilayer ceramic electronic component having excellent high-temperature withstand voltage characteristics.

[0014] One of the various advantages of the embodiments of the present invention is that it can provide dielectric and multilayer ceramic electronic components that can meet X5R or X7R requirements.

[0015] However, the various beneficial advantages and effects of the present invention are not limited to the above, and can be more easily understood in the course of describing specific embodiments of the present invention. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 2 is a schematic diagram illustrating the microstructure after sintering according to one embodiment of the present invention. [Figure 2] FIG. 2 is a cross-sectional view taken along line II' in FIG. [Figure 3] FIG. 3 is an enlarged view of region A in FIG. 2. [Figure 4] 1 is a scanning electron microscope (SEM) analysis photograph of a prototype sample of the present invention. [Figure 5] 1 is a scanning electron microscope (SEM) analysis photograph of a prototype sample of the present invention. [Figure 6] 1 is a scanning electron microscope (SEM) analysis photograph of a prototype sample of the present invention. [Figure 7] 1 shows the results of XRD analysis of a prototype sample of the present invention. [Figure 8] 1 is a graph showing the dielectric constant of a prototype sample of the present invention under a dc-bias field. [Figure 9] 1 is a graph showing the dielectric constant of a prototype sample of the present invention as a function of a dc-bias field at various temperatures. [Figure 10] 1 is a graph showing the contents of the third, fourth, and fifth subcomponents in an experimental example of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0017] Hereinafter, embodiments of the present invention will be described with reference to specific embodiments and the accompanying drawings. This should be understood as not limiting the technology described in this specification to specific embodiments, but as including various modifications, equivalents, and / or alternatives in the embodiments of the present invention. In the description of the drawings, similar reference numerals may be used for similar components.

[0018] In addition, in the drawings, in order to clearly explain the present invention, parts that are not relevant to the explanation are omitted, and thicknesses are shown exaggerated to clearly represent multiple layers and regions, and components having the same function within the same concept can be described using the same reference symbols.

[0019] In this specification, the terms "have," "can have," "include," or "can include" indicate the presence of a given feature (e.g., a value, function, operation, or component such as a part) and do not exclude the presence of additional features.

[0020] As used herein, expressions such as "A or B," "at least one of A and / or B," or "one or more of A and / or B" include all possible combinations of the items listed together. For example, "A or B," "at least one of A and B," or "at least one of A or B" can refer to (1) at least one A, (2) at least one B, or (3) both at least one A and at least one B.

[0021] In the drawings, the X direction can be defined as the first direction, L direction or length direction, the Y direction can be defined as the second direction, W direction or width direction, and the Z direction can be defined as the third direction, T direction or thickness direction.

[0022] The present invention relates to a dielectric, and the dielectric according to the present invention is applied to electronic components. Examples of electronic components including the dielectric of the present invention include, but are not limited to, capacitors, inductors, piezoelectric elements, varistors, thermistors, and the like.

[0023] The dielectric according to one embodiment of the present invention is (Ba 1-x Ca x )(Ti 1-y (Zr, Sn, Hf) y)O3 (where 0≦x≦1, 0≦y≦0.05), and the angle corresponding to the maximum peak in the XRD pattern of the (002) and (200) planes obtained using Cu Kα1 radiation (wavelength λ=1.5406 Å) is defined as θ0, and the angles corresponding to the full width at half maximum (FWHM) are defined as θ1 and θ2, respectively (where θ1<θ2), and (θ2-θ0) / (θ0-θ1) may be greater than 0.54 and not greater than 1.0.

[0024] In one example, the dielectric of the present invention may include grains and grain boundaries. Figures 1 to 3 are schematic diagrams illustrating the microstructure of a dielectric according to an embodiment of the present invention. The dielectric of the present invention may be formed by sintering the main component and the subcomponent described below. Furthermore, the dielectric formed by sintering the main component and the subcomponent may include grains 141 and grain boundaries 142.

[0025] Generally, dielectrics are required to have high dielectric constants, and research has been conducted to improve the crystallinity of dielectric compositions that constitute the dielectrics. Meanwhile, the inventors have discovered that the high electric field dc-bias dielectric constant changes depending on the tetragonality (c / a) of the crystal grains generated after sintering.

[0026] Three prototype MLCC samples were prepared and tested to confirm the relationship between the tetragonal ratio (c / a) of the crystal grains and the high-field dc-bias dielectric constant. Figures 4 to 6 show the microstructures of CG, FG, and FG-Ba, respectively. The crystal grain sizes confirmed in Figures 4 to 6 were 1740 nm, 251 nm, and 259 nm, respectively. Therefore, a comparison of Figures 4 (CG) and 5 (FG) reflects the difference due to crystal grain size, while a comparison of Figures 5 (FG) and 6 (FG-Ba) shows the results when different compositions are used under the same crystal grain size conditions.

[0027] Figure 7 shows the XRD patterns corresponding to the BaTiO3 (002) and (200) planes using Cu Kα1 radiation (wavelength λ = 1.5406 Å) for the powder samples CG, FG, and FG-Ba. The order of tetragonality (c / a) size is CG > FG > FG-Ba. CG shows clear peak separation for the (002) and (200) planes, while the two peaks partially overlap for FG and completely overlap for FG-Ba, confirming a nearly cubic structure.

[0028] Referring to FIG. 7, in the peaks of the XRD patterns of the (002) and (200) planes using Cu Kα1 radiation (wavelength λ=1.5406 Å) for CG, FG, and FG-Ba, when the angle corresponding to the maximum peak is θ0, and the angles corresponding to the full width at half maximum (FWHM) are θ1 and θ2 (where θ1<θ2), (θ2-θ0) is the ratio of the angle corresponding to the maximum peak and the full width at half maximum (FWHM) to the angle corresponding to the maximum peak. big Difference between the corresponding angle and the angle = B ) and (θ0-θ1) is (the half width small The difference between the angle corresponding to the maximum peak and the angle corresponding to the maximum peak = A ) In this case, it can be seen that as the tetragonality (c / a) increases from 1.004 (FG-Ba) to 1.007 (FG) and 1.009 (CG), the B / A value decreases.

[0029] Figure 8 shows the dc-bias field dielectric constants of CG, FG, and FG-Ba at room temperature. It can be seen that the dielectric constant at high dc fields of 8 V / μm or more increases as the grain size decreases from CG to FG. Furthermore, when comparing FG and FG-Ba under the same grain size, it can be seen that the dc high-field dielectric constant increases depending on the dielectric composition. This result indicates that the high-field dc-bias dielectric constant can be improved by changing the dielectric composition.

[0030] From the above results, it can be confirmed that as the tetragonality of the sintered dielectric decreases, the ratio (B / A) of (the difference between the angle corresponding to the maximum peak and the smallest angle of the half-width) / (the difference between the angle corresponding to the largest angle of the half-width and the angle corresponding to the maximum peak) increases for the peaks in the (002) and (200) planes of the XRD pattern using Cu Kα1 radiation (wavelength λ=1.5406 Å), and the high-field dc-bias dielectric constant improves. Furthermore, when the angle corresponding to the maximum peak in the XRD pattern using Cu Kα1 radiation (wavelength λ=1.5406 Å) is defined as θ0, and the angles corresponding to the full width at half maximum (FWHM) are defined as θ1 and θ2, respectively (where θ1<θ2), then (θ2-θ0) / (θ0-θ1)=(the angle corresponding to the maximum peak and the smallest angle of the half-width) big (difference between the angle and the corresponding angle) / (half width small When the difference between the angle corresponding to the maximum peak and the angle corresponding to the maximum peak (B / A) is greater than 0.54, it can be confirmed that the film has an excellent high electric field dc-bias dielectric constant.

[0031] The angle difference ratio (θ2-θ0) / (θ0-θ1)=B / A may be greater than 0.54, 0.55 or greater, 0.56 or greater, 0.57 or greater, or 0.58 or greater, and the upper limit may be, for example, 1 or less or less than 1, but is not limited thereto. When the angle difference ratio (θ2-θ0) / (θ0-θ1)=B / A satisfies the above range, the high electric field dc-bias permittivity can be improved.

[0032] A dielectric according to an embodiment of the present invention includes a major component and a minor component, and the minor component may include at least one of the first to sixth minor components. In this specification, the term "major component" may refer to a component that occupies a relatively large weight percentage compared to other components, and may refer to a component that accounts for 50 wt% or more based on the weight of the entire composition or the entire dielectric layer. Also, the term "minor component" may refer to a component that occupies a relatively small weight percentage compared to other components, and may refer to a component that accounts for less than 50 wt% based on the weight of the entire composition or the entire dielectric layer.

[0033] Each component of the dielectric according to one embodiment of the present invention will now be described in more detail.

[0034] a) Main component The dielectric according to one embodiment of the present invention is (Ba 1-x Ca x )(Ti 1-y (Zr, Sn, Hf) y )O3 (where 0≦x≦1, 0≦y≦0.05). The main component may be, for example, a chemical compound in which Ca, Zr, Sn, and / or Hf are partially dissolved in BaTiO3. In the composition formula, x may be in the range of 0 to 1, and y may be in the range of 0 to 0.05, but is not limited thereto. For example, when x is 0, y is 0, and z is 0 in the composition formula, the main component may be BaTiO3.

[0035] b) First subcomponent According to an embodiment of the present invention, the dielectric according to the present invention may include, as a first minor component, one or more selected from the group consisting of variable-valence acceptor elements, including one or more of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn, oxides thereof, and carbonates thereof.

[0036] The first minor component may be included in an amount of 0.1 molar parts or more and / or 1.0 molar parts or less relative to 100 molar parts of the main component. The content of the first minor component may be based on the content of at least one element selected from Mn, V, Cr, Fe, Ni, Co, Cu, and Zn included in the first minor component, regardless of the addition form, such as oxide or carbonate. For example, if the first minor component contains 0.1 molar parts of V2O5, an oxide of V, the total content of V may be 0.2 molar parts.

[0037] The first subcomponent improves the reduction resistance of the dielectric ceramic composition and also improves the high-temperature withstand voltage characteristics of the multilayer ceramic electronic component to which the dielectric is applied.

[0038] c) Second subcomponent According to an embodiment of the present invention, the dielectric according to the present invention may include, as a second minor component, one or more of fixed-valence acceptor elements including Mg, oxides thereof, and carbonates thereof.

[0039] The second minor component may be included in an amount of 2.0 molar parts or less relative to 100 molar parts of the main component. The content of the second minor component may be based on the content of Mg element contained in the second minor component, regardless of the addition form, such as oxide or carbonate. The lower limit of the second minor component is not particularly limited. For example, the second minor component may be 0 molar parts or more or more than 0 molar parts relative to 100 molar parts of the main component, but is not limited thereto.

[0040] If the content of the second minor component exceeds 2.0 parts by mole with respect to 100 parts by mole of the main component, the dielectric constant may be reduced, which may result in a problem of reduced high-temperature voltage resistance characteristics.

[0041] d) Third subcomponent According to one embodiment of the present invention, the dielectric according to the present invention may include a third minor component including one or more selected from the group consisting of one or more elements of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb, oxides thereof, and carbonates thereof.

[0042] The third minor component may be included in an amount of 0.3 molar parts or more and / or 5.4 molar parts or less relative to 100 molar parts of the main component. The content of the third minor component may be based on the content of at least one element selected from Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb included in the third minor component, regardless of the addition form such as oxide or carbonate.

[0043] In one embodiment of the present invention, the third subcomponent serves to prevent a decrease in reliability of a multilayer ceramic electronic component to which the dielectric is applied. If the third subcomponent is out of the above range, high-temperature withstand voltage characteristics may be degraded.

[0044] e) Fourth subcomponent According to one embodiment of the present invention, the dielectric according to the present invention may include a fourth minor component including at least one selected from the group consisting of at least one element of Ba and Ca, an oxide thereof, and a carbonate thereof.

[0045] The fourth minor component may be included in an amount of 5.0 molar parts or less relative to 100 molar parts of the main component. The lower limit of the fourth minor component may be, for example, 0 molar parts or more, relative to 100 molar parts of the main component. The content of the fourth minor component may be based on the content of at least one element selected from Ba and Ca included in the fourth minor component, regardless of the addition form, such as oxide or carbonate.

[0046] By including the fourth subcomponent in an amount of 5.0 parts by mole or less relative to 100 parts by mole of the main component, the crystal structure of the dielectric material according to the present invention can be adjusted.

[0047] f) Fifth subcomponent According to one embodiment of the present invention, the dielectric according to the present invention may include a fifth minor component including one or more selected from the group consisting of an oxide of Si element, a carbonate of Si element, and a glass containing Si element.

[0048] The fifth minor component may be included in an amount of 0.5 molar parts or more and / or 5.0 molar parts or less with respect to 100 molar parts of the main component. The content of the fifth minor component may be based on the content of Si element included in the fifth minor component, regardless of the addition form such as glass, oxide, or carbonate.

[0049] If the content of the fifth minor component is less than 0.5 parts by mole relative to 100 parts by mole of the main component, the dielectric constant and high-temperature withstand voltage may decrease, and if it is contained in an amount exceeding 5.0 parts by mole, problems such as a decrease in sinterability and density, and the generation of secondary phases may occur.

[0050] g) 6th subcomponent According to one embodiment of the present invention, the dielectric according to the present invention may include a sixth minor component including at least one selected from the group consisting of at least one element of Na and Li, an oxide thereof, and a carbonate thereof.

[0051] The sixth minor component may be contained in an amount of 1.0 molar part or less relative to 100 molar parts of the main component. The lower limit of the content of the sixth minor component may be, for example, 0 molar parts or more, or more than 0 molar parts relative to 100 molar parts of the main component.

[0052] The content of the sixth minor component may be based on the content of at least one element selected from Na and Li contained in the sixth minor component, regardless of the type of addition, such as glass, oxide, or carbonate. The sixth minor component may be included as a sintering aid, and may play a role in lowering the firing temperature.

[0053] In one example, the dielectric ceramic composition according to the present invention includes the third, fourth, and fifth subcomponents, and when the X-axis represents the content of the fifth subcomponent and the Y-axis represents the total content of the third and fourth subcomponents, the content relationship of the third, fourth, and fifth subcomponents can fall within the boundary and the interior of a rectangle connecting points A (0.500, 1.900), B (0.500, 3.10), C (5.000, 5.400), and D (5.000, 3.275).

[0054] 10 is a diagram showing the boundary and the interior of the quadrangle connecting the points A, B, C, and D. The boundary and the interior of the quadrangle connecting the points A, B, C, and D can be confirmed by the examples described later.

[0055] The present invention also relates to a multilayer ceramic electronic component.

[0056] FIG. 1 is a schematic perspective view showing a multilayer ceramic electronic component according to one embodiment of the present invention, FIG. 2 is a schematic cross-sectional view showing the multilayer ceramic electronic component taken along II' in FIG. 1, and FIG. 3 is an enlarged view of region A in FIG. 2.

[0057] 1 to 3, a multilayer ceramic electronic component 100 according to an embodiment of the present invention may include a ceramic body 110 including a dielectric layer 111, a first internal electrode 121, and a second internal electrode 122. A first external electrode 131 connected to the first internal electrode 121 and a second external electrode 132 connected to the second internal electrode 122 may be provided on an outer surface of the ceramic body 110.

[0058] Although there is no particular limitation on the specific shape of the ceramic body 110, as shown in the drawing, the ceramic body 110 may have a hexahedral shape or a similar shape. Due to shrinkage of the ceramic powder contained in the ceramic body 110 during the firing process, the ceramic body 110 may have a substantially hexahedral shape, although not a hexahedral shape with perfectly straight lines.

[0059] The ceramic body 110 can be formed by alternately stacking ceramic green sheets having a first internal electrode 121 printed on a dielectric layer 111 and ceramic green sheets having a second internal electrode 122 printed on a dielectric layer 111 in the thickness direction (Z direction).

[0060] The ceramic body 110 may have dielectric layers 111 and internal electrodes 121, 122 alternately stacked in a third direction. The plurality of dielectric layers 111 forming the ceramic body 110 may be in a sintered state, and may be integrated to such an extent that the boundary between adjacent dielectric layers 111 is difficult to identify without a scanning electron microscope (SEM).

[0061] According to an embodiment of the present invention, the dielectric layer 111 may be a layered structure of the dielectric material. 1-x Ca x )(Ti 1-y (Zr, Sn, Hf) y )O3 (where 0≦x≦1, 0≦y≦0.05). In addition to the main and subcomponents of the dielectric material, the material forming the dielectric layer 111 may contain various ceramic additives, organic solvents, plasticizers, binders, dispersants, etc., depending on the purpose of the present invention.

[0062] The dielectric layer 111 can be formed by adding additives as needed to a slurry containing the above-mentioned main and subcomponents, coating the slurry on a carrier film, and drying the coating to form a plurality of ceramic sheets. The ceramic sheets can be formed by cutting the slurry into sheets having a thickness of several μm using a doctor blade method, but are not limited thereto.

[0063] In the XRD pattern of the (002) and (200) planes using Cu Kα1 radiation (wavelength λ=1.5406 Å), the angle corresponding to the maximum peak is defined as θ0, and the angles corresponding to the full width at half maximum (FWHM) are defined as θ1 and θ2, respectively (where θ1<θ2), and (θ2-θ0) / (θ0-θ1) may be greater than 0.54 and equal to or less than 1.0. Details related to the XRD pattern have been described above and will not be repeated here.

[0064] The first and second internal electrodes 121 and 122 may be laminated such that their cross sections are exposed at opposite ends of the ceramic body 110. The material for forming the first and second internal electrodes 121 and 122 is not particularly limited, and may be formed using a conductive paste containing one or more of silver (Ag), palladium (Pd), gold (Au), platinum (Pt), nickel (Ni), copper (Cu), tin (Sn), tungsten (W), titanium (Ti), and alloys thereof. The conductive paste may be printed by screen printing or gravure printing, but the present invention is not limited thereto.

[0065] In a multilayer ceramic electronic component according to an embodiment of the present invention, a first external electrode 131 and a second external electrode 132 may be disposed on an outer surface of a 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.

[0066] The first external electrode 131 and the second external electrode 132 may include a conductive metal, which may be, but is not limited to, one or more of copper (Cu), nickel (Ni), tin (Sn), palladium (Pd), platinum (Pt), gold (Au), silver (Ag), tungsten (W), titanium (Ti), lead (Pb), and alloys thereof.

[0067] In another example of the present invention, the subcomponents of the multilayer ceramic electronic component according to the present invention include a first subcomponent containing one or more compounds selected from the group consisting of variable valence acceptor elements including one or more of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn, oxides thereof, and carbonates thereof; a second subcomponent containing one or more compounds selected from the group consisting of fixed valence acceptor elements including Mg, oxides thereof, and carbonates thereof; and one or more elements 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. The glass may contain at least one of a third subcomponent containing one or more compounds selected from the group consisting of one or more elements selected from Ba and Ca, their oxides, and their carbonates; a fourth subcomponent containing one or more compounds selected from the group consisting of one or more elements selected from Ba and Ca, their oxides, and their carbonates; a fifth subcomponent containing one or more compounds selected from the group consisting of an oxide of Si, a carbonate of Si, and a glass containing Si; and a sixth subcomponent containing one or more compounds selected from the group consisting of one or more elements selected from Na and Li, their oxides, and their carbonates.

[0068] In still another example of the present invention, the minor components of the multilayer ceramic electronic component include a third minor component containing one or more compounds selected from the group consisting of one or more elements of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb, oxides thereof, and carbonates thereof; a fourth minor component containing one or more compounds selected from the group consisting of one or more elements of Ba and Ca, oxides thereof, and carbonates thereof; and an oxide of Si element. , a carbonate of Si element, and a glass containing Si element; and a fifth minor component including one or more compounds selected from the group consisting of: a carbonate of Si element, a carbonate of Si element, and a glass containing Si element. When the X-axis is the content of the fifth minor component and the Y-axis is the total content of the third minor component and the fourth minor component, the content relationship of the third, fourth, and fifth minor components can belong to the boundary and the interior of a rectangle connecting points A (0.500, 1.900), B (0.500, 3.100), C (5.000, 5.400), and D (5.000, 3.275).

[0069] The dielectric, main components, and subcomponents are the same as those of the dielectric according to the embodiment of the present invention, and therefore will not be described here. Furthermore, although a multilayer ceramic capacitor is used as an example of a multilayer ceramic electronic component in this specification, the multilayer ceramic electronic component is not limited thereto.

[0070] The present invention will be explained in more detail below by giving experimental examples. However, these examples are intended to aid in the concrete understanding of the invention, and the scope of the present invention is not limited to these experimental examples.

[0071] Experimental example BaTiO3 powder with an average particle size of 100 nm was used as the raw material for the main component. The raw material powders of the main and subcomponents, corresponding to compositions 1-1 to 5-3 shown in Table 1 below, were mixed with ethanol / toluene and a dispersant and milled for 10 hours using zirconia balls as a mixing / dispersion medium. A binder was then mixed into the mixture and milled for an additional 10 hours.

[0072] Examples 1-2-A, 1-2-B, and 1-2-C shown in Table 1 indicate examples in which the milling time before adding the binder was increased to 20, 30, and 40 hours in order to reduce the tetragonality (c / a) of the dielectric, that is, to increase the B / A of the XRD peak of the (002) / (200) plane.

[0073] The produced slurry was used to produce sheets with thicknesses of 0.8 μm and 10 μm using a thin-layer sheet production machine, and Ni internal electrodes were printed on the sheets.

[0074] The upper and lower covers were fabricated by laminating 25 layers of cover sheets (10-13 μm thick), and 21 layers of printed active sheets were laminated under pressure to fabricate a bar.

[0075] The crimped bar was cut into 3.2mm x 1.6mm chips using a cutting machine. The completed 3216 size MLCC chips were calcined and then fired in a reducing atmosphere of 0.1% H2 / 99.9% N2 to 1.0% H2 / 99.0% N2 (H2O / H2 / N2 atmosphere) at temperatures of 1080 to 1120°C for a holding time of 10 minutes to 1 hour, and then re-oxidized at 950°C in an N2 atmosphere for 3 hours.

[0076] The fired chip was then subjected to a termination process using Cu paste and electrode firing to complete the external electrodes, resulting in a 3.2mm x 1.6mm MLCC chip with a dielectric thickness of approximately 0.6μm after firing and 20 dielectric layers.

[0077] The room temperature capacitance and dielectric loss of the MLCC chip were measured using an LCR meter at 1 kHz and AC 0.5 V / μm. The dielectric constant of the MLCC chip dielectric was calculated from the capacitance, thickness of the MLCC chip dielectric, area of ​​the internal electrodes, and number of layers.

[0078] The room temperature insulation resistance was measured after 60 seconds of applying DC 10V / μm to 10 samples.

[0079] The change in capacitance with temperature was measured in the temperature range from -55°C to 145°C.

[0080] The high-temperature IR boosting experiment measured the resistance degradation behavior while increasing the voltage step by 10V / μm at 150℃, with each step lasting 1 hour and the resistance measured at 5-second intervals. The high-temperature withstand voltage was also derived from the high-temperature IR boosting experiment. A voltage step of 5V / μm DC was applied to a 3216-size chip with 20 dielectric layers, each with a thickness of 0.6μm after firing, at 150℃ for 1 hour. The voltage step was continuously increased while measurements were taken. The IR was 10 6 This means that the voltage it can withstand is more than Ω.

[0081] Table 2 shows the characteristics of the prototype chip corresponding to the embodiment specified in Table 1.

[0082] [Table 1]

[0083] [Table 2]

[0084] In the characteristic evaluation in Table 2 above and Table 4 below, cases where all of the following conditions were met were indicated by ○: dc bias high electric field permittivity @ 8 V / μm (permittivity when dc 8 V / μm is applied) 1000 or more, high temperature (150°C) withstand voltage 50 V / μm or more, and TCC (85°C) less than 13.5%, and cases where even one of the conditions was not met were indicated by ×.

[0085] Examples 1-1 to 1-4 in Table 1 show examples where the sum of the variable valence elements (Mn, V) as the first minor component is fixed at 0.3 mol, the content of Mg as the second minor component is fixed at 0 mol, the content of the rare earth element Dy as the third minor component is fixed at 0.3 mol, the content of Si as the fifth minor component is fixed at 0.5 mol, and the sum of the elements (Na, Li) as the sixth minor component is fixed at 0.4 mol, relative to 100 mol of the main component raw material BaTiO3 of 80 nm size. Examples 1-1 to 1-4 in Table 2 show the characteristics of prototype MLCC samples corresponding to these examples.

[0086] At a low Ba content of 1.2 moles (Example 1-1), the B / A ratio of the (002) / (200) XRD peak was as low as 0.50, indicating a low high-field dielectric constant of less than 1000. When the Ba content was increased to 2.0 moles (Example 1-2), the B / A ratio of the XRD peak increased to 0.58, achieving the target properties of the present invention: a dc bias high-field dielectric constant @ 8 V / μm (dielectric constant when a dc voltage of 8 V / μm is applied) of 1000 or more, a high-temperature (150°C) withstand voltage of 50 V / μm or more, and a TCC (85°C) of less than ±15%. Even when the same amount of Ca was used instead of Ba (Example 1-3), nearly identical properties to those of Example 1-2 were achieved. When the Ba content was further increased to 2.8 mol (Example 1-4), B / A further increased to 0.92, and the dc bias high electric field dielectric constant @ 8V / μm further increased to 1115.

[0087] Examples 2-1 to 2-3 in Table 1 show examples in which the fourth minor component Ba is varied under the conditions that the sum of the first minor component variable valence elements (Mn, V) is 0.3 mol, the content of the second minor component Mg is 0.2 mol, the content of the third minor component rare earth element Dy is 0.3 mol, the content of the fifth minor component Si is 1.25 mol, and the sum of the sixth minor component (Na, Li) is 1.0 mol, relative to 100 mol of the 80 nm sized main component raw material BaTiO3. Table 2, 2-1 to 2-3, show the characteristics of prototype MLCC samples corresponding to these examples.

[0088] At a low Ba content of 1.6 moles (Example 2-1), the B / A ratio of the XRD peak for the (002) / (200) plane was 0.51, indicating a low high-field dielectric constant of less than 1000. When the Ba content was increased to 2.4 moles (Example 2-2), the B / A ratio of the XRD peak increased to 0.63, simultaneously achieving the target properties of the present invention: a dc bias high-field dielectric constant @ 8 V / μm (dielectric constant when dc 8 V / μm is applied) of 1000 or more, a high-temperature (150°C) withstand voltage of 50 V / μm or more, and a TCC (85°C) of less than ±15%. When the Ba content was further increased to 3.2 moles (Example 2-3), the B / A ratio of the XRD peak increased to 0.82, and the dc bias high-field dielectric constant @ 8 V / μm also increased to 1102.

[0089] Examples 3-1 to 3-3 in Table 1 show examples where the fourth minor component Ba is varied under the following conditions: the sum of the first minor component variable valence elements (Mn, V) is 0.3 mol, the content of the second minor component Mg is 0.2 mol, the content of the third minor component rare earth element Dy is 1.4 mol, the content of the fifth minor component Si is 2.75 mol, and the sum of the sixth minor component (Na, Li) is fixed at 0.4 mol, relative to 100 mol of the 80 nm sized main component raw material BaTiO3. Table 2, 3-1 to 3-3, show the characteristics of prototype MLCC samples corresponding to these examples.

[0090] At a low Ba content of 1.2 moles (Example 3-1), the B / A ratio of the (002) / (200) XRD peak was 0.48, indicating a low high-field dielectric constant of less than 1000. When the Ba content was increased to 2.0 moles (Example 3-2), the B / A ratio of the XRD peak increased to 0.66, simultaneously achieving the target properties of the present invention: a dc bias high-field dielectric constant @ 8 V / μm (dielectric constant when dc 8 V / μm is applied) of 1000 or more, a high-temperature (150°C) withstand voltage of 50 V / μm or more, and a TCC (85°C) of less than ±15%. When the Ba content was further increased to 2.8 moles, the B / A ratio of the XRD peak increased to 0.82, and the dc bias high-field dielectric constant @ 8 V / μm also increased to 1123.

[0091] Examples 4-1 to 4-4 in Table 1 show examples in which the fourth minor component Ba is varied under the conditions that the sum of the first minor component variable valence elements (Mn, V) is 0.3 moles, the content of the second minor component Mg is 2.0 moles, the content of the third minor component rare earth element Dy is 1.0 mole, and the content of the fifth minor component Si is 3.38 moles, relative to 100 moles of the 80 nm sized main component raw material. Table 2 shows the characteristics of prototype MLCC samples corresponding to these examples.

[0092] When the Ba content was low (1.85 moles) (Example 4-1), the B / A ratio of the (002) / (200) plane XRD peak was 0.48, indicating a low high-field dielectric constant of less than 1000. When the Ba content was increased to 2.7 moles (Example 4-2), the B / A ratio of the XRD peak increased to 0.60, simultaneously achieving the target properties of the present invention: a dc bias high-field dielectric constant @ 8 V / μm (dielectric constant when dc 8 V / μm is applied) of 1000 or more, a high-temperature (150°C) withstand voltage of 50 V / μm or more, and a TCC (85°C) of less than ±15%. Even when the same amount of Ca was used instead of Ba (Example 4-3), nearly identical properties to those of Example 4-2 were achieved. When the Ba content was further increased to 3.65 mol, the B / A ratio of the XRD peak further increased to 0.82, and the dc bias high electric field dielectric constant @ 8 V / μm further increased to 1133.

[0093] Examples 5-1 to 5-3 in Table 1 show examples in which the fourth minor component Ba is varied under the conditions that the sum of the first minor component variable valence elements (Mn, V) is 1.0 mole, the content of the second minor component Mg is 1.0 mole, the content of the third minor component rare earth element Dy is 1.0 mole, and the content of the fifth minor component Si is 5.00 mole, relative to 100 moles of the 80 nm sized main component raw material BaTiO3. Table 2 shows the characteristics of prototype MLCC samples corresponding to these examples.

[0094] When the Ba content was low (2.4 moles) (Example 5-1), the B / A ratio of the XRD peak for the (002) / (200) plane was 0.52, indicating a low high-field dielectric constant of less than 1000. When the Ba content was increased to 3.4 moles (Example 5-2), the B / A ratio of the XRD peak increased to 0.61, simultaneously achieving the target properties of the present invention: a dc bias high-field dielectric constant @ 8 V / μm (dielectric constant when dc 8 V / μm is applied) of 1000 or more, a high-temperature (150°C) withstand voltage of 50 V / μm or more, and a TCC (85°C) of less than ±15%. When the Ba content was further increased to 4.4 moles, the B / A ratio of the XRD peak increased to 0.85, and the dc bias high-field dielectric constant @ 8 V / μm further increased to 1098.

[0095] Examples 1-2-A to 1-2-C in Table 1 show examples of batch slurry mixing milling time changes when subcomponents corresponding to Example 1-2 are applied to 100 moles of 80 nm sized main component raw material BaTiO3, and 1-2-A to 1-2-C in Table 2 show the properties of prototype MLCC samples corresponding to these examples.

[0096] The mixed milling 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 mixed milling time increased to 10, 15, and 20 hours, the B / A ratio of the (002) / (200) XRD peak increased to 0.58, 0.70, and 0.85, respectively, while the dc bias high-field dielectric constant @ 8 V / μm increased to 1018, 1084, and 1103. Therefore, in addition to adjusting the composition of the minor additives, increasing the mixed milling time to decrease the tetragonality (c / a) of the dielectric and increase the B / A ratio of the XRD peak can also improve the dc bias high-field dielectric constant @ 8 V / μm. On the other hand, excessively increasing the mixed milling time to 30 hours resulted in a rapid increase in the crystal grain size of the dielectric, resulting in a decrease in the B / A ratio of the (002) / (200) XRD peak. This results in a rapid drop in the dc bias high field permittivity @ 8V / μm to 726.

[0097] [Table 3]

[0098] [Table 4]

[0099] Examples 6 to 14 in Table 3 show examples where the subcomponents corresponding to Examples 1 and 2 are applied and the composition of the 100 nm-sized main component raw material is changed, and Examples 6 to 14 in Table 4 show the characteristics of the prototype MLCC samples corresponding to these examples.

[0100] When a portion of Ti was replaced with Zr, as the Zr content increased from 0 at%, 2 at%, to 5 at%, (Examples 1-2, 6, 7, and 8), the B / A ratio of the XRD peak of the (002) / (200) plane increased to 0.58, 0.71, and 0.84, and the dc bias high-field dielectric constant at 8 V / μm increased to 1018, 1117, and 1205, while the TCC at 85°C decreased to -11.8%, -12.6%, and -14.7%. Therefore, in addition to adjusting the composition of the minor additive, substituting a portion of the Ti element in the main component with Zr can also improve the dc bias high-field dielectric constant at 8 V / μm by increasing the B / A ratio of the XRD peak of the dielectric (002) / (200) plane. On the other hand, if the Zr content is excessively increased to 7 at%, the B / A ratio of the XRD peak further increases, the dc bias high electric field dielectric constant @ 8 V / μm further increases to 1284, but the TCC at 85°C also increases further to -18.4%, resulting in a problem of not being able to satisfy the TCC characteristics. Therefore, it can be confirmed that the target characteristics of the present invention can be achieved when the Zr content in the main composition is in the range of 0 to 5 at%.

[0101] Examples 9 to 11 and Examples 12 to 14 in Table 3 show examples in which a portion of the main component Ti is replaced with Sn and Hf, and the contents thereof are increased to 2 at%, 5 at%, and 7 at%, respectively. Examples 9 to 11 and Examples 12 to 14 in Table 4 show the properties of prototype MLCC samples corresponding to these examples.

[0102] As with the Zr substitution, as the content increases to 2 at% and 5 at% the 85°C TCC decreases within the specification range, the B / A ratio of the (002) / (200) XRD peak increases, and the dc bias high-field dielectric constant @ 8 V / μm increases. On the other hand, when the Sn or Hf content is excessively increased to 7 at%, the B / A ratio of the XRD peak increases further, and the dc bias high-field dielectric constant @ 8 V / μm increases further. However, the X5R TCC characteristic required for the 85°C TCC to be ±15% or less cannot be met. Therefore, it can be confirmed that the target characteristics of the present invention can be achieved when the Zr, Sn, or Hf content in the main composition is in the range of 0 to 5 at%.

[0103] In addition, through Examples 1-4, 2-3, 3-3, 4-4, and 5-3, the boundary values ​​of the total contents of the third and fourth minor components relative to the content of the fifth minor component shown in FIG. 10 can be confirmed. It can be confirmed that Examples 1-1, 2-1, 3-1, 4-1, and 5-1 do not satisfy the characteristic evaluation, while Examples 1-2, 2-2, 3-2, 4-2, and 5-2 satisfy the characteristic evaluation. Therefore, it can be confirmed that the characteristic evaluation changes at the intermediate values ​​between Examples 1-1, 2-1, 3-1, 4-1, and 5-1 and Examples 1-2, 2-2, 3-2, 4-2, and 5-2, and therefore the intermediate values ​​of the above examples were determined as the boundary values. It can be confirmed that excellent high-temperature withstand voltage and high-field dc-bias characteristics are exhibited when the content ranges of the third, fourth, and fifth minor components fall within and within the boundary of the rectangle connecting A, B, C, and D in FIG. 10. [Explanation of symbols]

[0104] 100 Multilayer ceramic electronic components 110 Ceramic body 111 Dielectric layer 121, 122 First and second internal electrodes 131, 132 First and second external electrodes 141 Crystal Grains 142 Grain Boundaries

Claims

1. (Ba １－ｘ Ca ｘ ) (Ti １－ｙ (Zr, Sn, Hf) ｙ ) O ３ (where 0≦x≦1, 0≦y≦0.05), The angle corresponding to the maximum peak in the XRD pattern peaks of the (002) and (200) planes using Cu Kα1 radiation (wavelength λ = 1.5406 Å) was defined as θ ０ The angle corresponding to the full width at half maximum (FWHM) is defined as θ １ and θ ２ When (however, θ １ <θ ２ ), (θ ２ -θ ０ ) / (θ ０ -θ １ ) is greater than 0.54 and less than or equal to 1.0, The subcomponent includes a sixth subcomponent, and the sixth subcomponent includes at least one or more compounds selected from the group consisting of Li, an oxide of Li, and a carbonate of Li, and one or more compounds selected from the group consisting of Na, an oxide of Na, and a carbonate of Na.

2. The dielectric of claim 1 , comprising grains and grain boundaries.

3. The subcomponent is a first subcomponent including one or more compounds selected from the group consisting of variable valence acceptor elements including one or more of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn, oxides thereof, and carbonates thereof; a second subcomponent including one or more compounds of fixed valence acceptor elements including Mg, oxides thereof, and carbonates thereof; a third subcomponent containing one or more compounds selected from the group consisting of one or more elements of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb, oxides thereof, and carbonates thereof; a fourth subcomponent containing one or more compounds selected from the group consisting of one or more elements of Ba and Ca, oxides thereof, and carbonates thereof; and a fifth subcomponent containing one or more compounds selected from the group consisting of an oxide of Si element, a carbonate of Si element, and a glass containing Si element.

4. The subcomponents include a first subcomponent including one or more compounds selected from the group consisting of variable valence acceptor elements including one or more of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn, oxides thereof, and carbonates thereof; 3. The dielectric according to claim 1, wherein the first subcomponent is contained in an amount of 0.1 part by mol or more and 1.0 part by mol or less relative to 100 parts by mol of the main component.

5. the subcomponent includes a second subcomponent including one or more compounds of fixed valence acceptor elements including Mg, oxides thereof, and carbonates thereof; 3. The dielectric according to claim 1, wherein the second subcomponent is contained in an amount of 2.0 parts by mol or less relative to 100 parts by mol of the main component.

6. the subcomponents include a third subcomponent containing one or more compounds selected from the group consisting of one or more elements of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb, oxides thereof, and carbonates thereof; 3. The dielectric according to claim 1, wherein the third subcomponent is contained in an amount of 0.3 parts by mol or more and 5.4 parts by mol or less relative to 100 parts by mol of the main component.

7. The subcomponents include a fourth subcomponent containing one or more compounds selected from the group consisting of one or more elements of Ba and Ca, oxides thereof, and carbonates thereof, 3. The dielectric according to claim 1, wherein the fourth subcomponent is contained in an amount of 5.0 parts by mol or less relative to 100 parts by mol of the main component.

8. the subcomponents include a fifth subcomponent including one or more compounds selected from the group consisting of an oxide of Si element, a carbonate of Si element, and a glass containing Si element; 3. The dielectric according to claim 1, wherein the fifth subcomponent is contained in an amount of 0.5 parts by mol or more and 5.0 parts by mol or less relative to 100 parts by mol of the main component.

9. A dielectric as described in claim 1 or 2, containing the sixth minor component in a range of 1.0 molar part or less per 100 molar parts of the main component.

10. The subcomponent is a third subcomponent containing one or more compounds selected from the group consisting of one or more elements of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb, oxides thereof, and carbonates thereof; a fourth subcomponent containing one or more compounds selected from the group consisting of one or more elements of Ba and Ca, oxides thereof, and carbonates thereof; a fifth subcomponent including one or more compounds selected from the group consisting of an oxide of Si element, a carbonate of Si element, and a glass including Si element; 3. The dielectric according to claim 1 or 2, wherein when the X-axis represents the content of the fifth minor component and the Y-axis represents the total content of the third minor component and the fourth minor component, the content relationship of the third, fourth, and fifth minor components falls within the boundary of a rectangle connecting points A (0.500, 1.900), B (0.500, 3.100), C (5.000, 5.400), and D (5.000, 3.275).

11. a ceramic body including a dielectric layer, a first internal electrode, and a second internal electrode; a first external electrode and a second external electrode disposed on an outer surface of the ceramic body and connected to the first internal electrode and the second internal electrode, respectively; The dielectric layer is made of (Ba １－ｘ Ca ｘ ) (Ti １－ｙ (Zr, Sn, Hf) ｙ ) O ３ (where 0≦x≦1, 0≦y≦0.05), The angle corresponding to the maximum peak in the XRD pattern peaks of the (002) and (200) planes using Cu Kα1 radiation (wavelength λ = 1.5406 Å) was defined as θ ０ The angle corresponding to the full width at half maximum (FWHM) is defined as θ １ and θ ２ When (however, θ １ <θ ２ ), (θ ２ -θ ０ ) / (θ ０ -θ １ ) is greater than 0.54 and less than or equal to 1.0, the subcomponents include a sixth subcomponent, the sixth subcomponent including at least one compound selected from the group consisting of Li, an oxide of Li, and a carbonate of Li, and one or more compounds selected from the group consisting of Na, an oxide of Na, and a carbonate of Na.

12. The subcomponent is a first subcomponent including one or more compounds selected from the group consisting of variable valence acceptor elements including one or more of Mn, V, Cr, Fe, Ni, Co, Cu, and Zn, oxides thereof, and carbonates thereof; a second subcomponent including one or more compounds of fixed valence acceptor elements including Mg, oxides thereof, and carbonates thereof; a third subcomponent containing one or more compounds selected from the group consisting of one or more elements of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb, oxides thereof, and carbonates thereof; a fourth subcomponent containing one or more compounds selected from the group consisting of one or more elements of Ba and Ca, oxides thereof, and carbonates thereof; and a fifth subcomponent containing one or more compounds selected from the group consisting of an oxide of Si element, a carbonate of Si element, and a glass containing Si element.

13. The subcomponent is a third subcomponent containing one or more compounds selected from the group consisting of one or more elements of Y, Dy, Ho, Er, Gd, Ce, Nd, Sm, Tb, Tm, La, Gd, and Yb, oxides thereof, and carbonates thereof; a fourth subcomponent containing one or more compounds selected from the group consisting of one or more elements of Ba and Ca, oxides thereof, and carbonates thereof; a fifth subcomponent including one or more compounds selected from the group consisting of an oxide of Si element, a carbonate of Si element, and a glass including Si element; 12. The multilayer ceramic electronic component according to claim 11, wherein when the X-axis represents the content of the fifth minor component and the Y-axis represents the total content of the third minor component and the fourth minor component, the content relationship of the third, fourth, and fifth minor components falls within and on the boundary of a quadrangle connecting points A (0.500, 1.900), B (0.500, 3.100), C (5.000, 5.400), and D (5.000, 3.275).

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