Multilayer ceramic electronic component

Abstract

This invention relates to a laminated ceramic electronic component. The laminated ceramic electronic component has a component body formed by stacking a dielectric layer and an internal electrode layer. The dielectric layer has main phase particles. The component body has segregation. The main phase particles contain, on an atomic basis, a component with the formula (Ca...). 1‑x‑p Sr x Ba p ) m (Zr 1‑y‑z Ti y Hf z The perovskite compound represented by O3 is the main component. It satisfies the following conditions: 0 ≤ x ≤ 1.0, 0 ≤ p < 1.0, 0.9 ≤ m ≤ 1.1, 0 ≤ y ≤ 0.20, and 0 ≤ z < 1.0. The main phase particles also contain oxides of Z. Z is selected from one or more of V, Nb, Ta, and W. Segregation contains at least L, Mn, Si, and O. L is selected from one or more of Ca and Sr. The proportion of Z in the main phase particles is greater than the proportion of Z in the segregation.

Description

Technical Field

[0001] This invention relates to a laminated ceramic electronic component. Background Technology

[0002] Patent Document 1 describes an invention related to a reduction-resistant dielectric ceramic composition and a multilayer ceramic capacitor, wherein the multilayer ceramic capacitor is formed by alternately stacking ceramic sheets made of the reduction-resistant dielectric ceramic composition and electrodes.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2007-91588 Summary of the Invention

[0006] The technical problem that the invention aims to solve

[0007] The purpose of this invention is to provide a multilayer ceramic electronic component that maintains good high-temperature resistivity while exhibiting excellent reliability.

[0008] Technical solutions for solving technical problems

[0009] To achieve the above objectives, the stacked ceramic electronic component of the present invention is a stacked ceramic electronic component having a component body formed by stacking a dielectric layer and an internal electrode layer, wherein,

[0010] The dielectric layer has main phase particles.

[0011] The main body of the component has segregation.

[0012] The main phase particles contain, on an atomic basis, the composition of the formula (Ca). 1-x-p Sr x Ba p ) m (Zr 1-y-z Ti y Hf z The perovskite compound represented by O3 is the main component.

[0013] Satisfying 0 ≤ x ≤ 1.0, 0 ≤ p < 1.0, 0.9 ≤ m ≤ 1.1, 0 ≤ y ≤ 0.20, and 0 ≤ z < 1.0,

[0014] The main phase particles also contain oxides of Z.

[0015] Z is selected from one or more of V, Nb, Ta, and W.

[0016] The segregation contains at least L, Mn, Si, and O.

[0017] L is selected from one or more of Ca and Sr.

[0018] The proportion of Z in the main phase particles is greater than the proportion of Z in the segregation.

[0019] Alternatively, it could satisfy 0≤x<0.80, 0≤p<0.40, 0.9<m<1.1, 0≤y≤0.10, and 0≤z<0.20.

[0020] Alternatively, it could satisfy 0≤x<0.40, p=0, 0.9<m<1.1, 0.01<y≤0.10, and 0≤z<0.20.

[0021] Alternatively, the proportion of Z contained in the main phase particles relative to the total content of all elements contained in the main phase particles can be defined as Zm based on the number of atoms.

[0022] The proportion of Z contained in the segregation relative to the total content of all elements contained in the segregation is defined as Zs based on the number of atoms.

[0023] 1.5 < Zm / Zs < 7.5.

[0024] Alternatively, in the segregation, the value obtained by dividing the content of Z by the total content of Z and Si, based on the atomic number, is greater than 0.0002 and less than 0.0080.

[0025] Alternatively, in the segregation, the value obtained by dividing the content of Z by the total content of Z and Mn, based on the atomic number, is greater than 0.003 and less than 0.080.

[0026] Alternatively, in the segregation, the value obtained by dividing the Mn content by the total Si and Mn content, based on the atomic number, is greater than 0.02 and less than 0.50.

[0027] Alternatively, in the segregation, the value obtained by dividing the content of Z by the total content of Z and Ni, based on the atomic number, is greater than 0 and less than 0.060.

[0028] Alternatively, in the segregation, the total content of Ca and Sr divided by the total content of Zr and Ti, based on the atomic number, is 1.0 or more and 8.0 or less.

[0029] Alternatively, the segregation may contain one or more oxides selected from Al, Mg, Li, B, and P.

[0030] Alternatively, the main component of the conductive material contained in the internal electrode layer may be Ni or a Ni-based alloy. Attached Figure Description

[0031] Figure 1 This is a schematic diagram showing a cross-section of a multilayer ceramic capacitor according to one embodiment of the present invention.

[0032] Figure 2 This is a STEM image showing segregation located inside the dielectric layer.

[0033] Figure 3 A STEM image showing the segregation at the boundary between the dielectric layer and the internal electrode layer.

[0034] Figure 4 This is a STEM image showing the segregation located in the inner electrode layer.

[0035] Explanation of reference numerals in the attached figures

[0036] 1. Multilayer ceramic capacitor

[0037] 2. Dielectric layer

[0038] 3 Internal electrode layer

[0039] 4 External Electrodes

[0040] 10 Components

[0041] 12. Separation Detailed Implementation

[0042] The present invention will now be described based on specific embodiments.

[0043] exist Figure 1 The image shows a multilayer ceramic capacitor 1, which is an example of an electronic component according to this embodiment. The multilayer ceramic capacitor 1 has a component body 10 with a structure formed by alternately stacking dielectric layers 2 and internal electrode layers 3. A pair of external electrodes 4 are formed at both ends of the component body 10, and the pair of external electrodes 4 are respectively connected to the internal electrode layers 3 alternately arranged inside the component body 10. The shape of the component body 10 is not particularly limited, and it is usually set to a cuboid shape. Furthermore, the size of the component body 10 is not particularly limited, as long as it is set to an appropriate size according to the application.

[0044] The dielectric layer 2 contains main phase particles, which will be described later. The thickness of each layer of the dielectric layer 2 (interlayer thickness) is particularly limited and can be arbitrarily set according to desired characteristics and applications. Typically, the interlayer thickness is preferably 30 μm or less, and more preferably 10 μm or less. In addition, the number of layers of the dielectric layer 2 is not particularly limited, but in this embodiment, for example, 20 or more is preferred.

[0045] The internal electrode layer 3 is stacked in such a way that each end face is alternately exposed on the surfaces of two opposite ends of the element body 10.

[0046] The main component of the conductive material contained in the internal electrode layer 3 is a metal. There are no particular limitations on the metal used; for example, any well-known conductive material such as Pd, Pd-based alloys, Pt, Pt-based alloys, Ni, Ni-based alloys, Cu, or Cu-based alloys can be used. The preferred main component metal is Ni or a Ni-based alloy. The metal may also contain trace amounts of P, S, Cl, etc., at approximately 0.1% by mass or less. The internal electrode layer 3 can also be formed using commercially available electrode paste. The thickness of the internal electrode layer 3 can be appropriately determined based on the intended application.

[0047] There are no particular limitations on the conductive material contained in the external electrode 4. For example, any known conductive material such as Ni, Cu, Sn, Ag, Pd, Pt, Au, or their alloys, or conductive resins, may be used. The thickness of the external electrode 4 may be appropriately determined according to the application.

[0048] The main phase particles contained in dielectric layer 2 have a composition based on the atomic number formula (Ca). 1-x-p Sr x Ba p ) m (Zr 1-y-z Ti y Hf z The perovskite compound represented by O3 is used as the main component. Moreover, it satisfies 0≤x≤1.00, 0≤p<1.00, 0.9≤m≤1.1, 0≤y≤0.20, and 0≤z<1.00.

[0049] It can also satisfy 0≤x<0.80, 0≤p<0.40, 0.9<m<1.1, 0≤y≤0.10, and 0≤z<0.20.

[0050] It can also satisfy 0≤x<0.40, p=0, 0.9<m<1.1, 0.01<y≤0.10, and 0≤z<0.20.

[0051] Furthermore, it is also possible to satisfy 0.01 < y ≤ 0.07. Alternatively, it is also possible to satisfy 0 ≤ z ≤ 0.01.

[0052] Perovskite compounds are compounds with a perovskite-type crystal structure represented by the general formula ABO3 (where A is the A-site element and B is the B-site element).

[0053] As described above, the perovskite compound of this embodiment contains at least Ca and / or Sr as A-site elements. It also contains at least Zr and / or Ti as B-site elements. Ba may also be contained as A-site elements, and Hf may also be contained as B-site elements.

[0054] In addition to the perovskite compounds mentioned above, the main phase particles also contain oxides of additive elements. The oxides of these additive elements contain at least one oxide of Z. Z is selected from V, Nb, Ta, and W. The main phase particles also contain L, Mn, Si, and O. L is selected from Ca and Sr. The main phase particles may also contain oxides of L, Mn, and Si.

[0055] The main body 10 of the component has a dielectric layer 2 and an internal electrode layer 3, and the main body 10 of the component also has segregation 12.

[0056] There are no particular restrictions on the position of the segregation 12 in the main body 10 of the component. Figures 2-4 This is a STEM image obtained by observing a cross-section of the main body 10 of the component cut along the stacking direction. For example... Figure 2 As shown, segregation 12 can also be located inside dielectric layer 2. For example... Figure 3 As shown, segregation 12 can also be located at the boundary between dielectric layer 2 and internal electrode layer 3. For example... Figure 4 As shown, segregation 12 can also be located in the inner electrode layer 3. That is, segregation 12 can also be located in the part of the cross-section where the inner electrode is interrupted.

[0057] The area of ​​segregation 12 is set to 1 μm. 2 That's all. In other words, areas smaller than 1μm... 2 The part is considered as partial analysis 12.

[0058] Furthermore, the proportion of Z in the main phase particles is greater than that in segregation 12. Specifically, if the proportion of Z in the main phase particles relative to the total content of all elements in the main phase particles is defined as Zm (based on atomic number), and the proportion of Z in segregation 12 relative to the total content of all elements in segregation 12 is defined as Zs (based on atomic number), then Zm / Zs > 1.0 or Zm / Zs ≥ 1.1. Preferably, 1.5 < Zm / Zs < 7.5. This structure improves reliability while maintaining good high-temperature resistivity.

[0059] When determining the Z content in the main phase particles, at least 10 measurement sites can be set for the main phase particles, and the Z content calculated at each measurement site can be averaged. Similarly, when determining the Z content in segregation 12, at least 10 measurement sites can be set at the center of segregation 12 (the portion at a distance of 0.5 μm or more from the outer periphery of segregation 12), and the Z content calculated at each measurement site can be averaged.

[0060] In segregation 12, based on the atomic number, the value obtained by dividing the Z content by the total Z and Si content can also be greater than 0.0002 and less than 0.0080.

[0061] In segregation 12, based on the atomic number, the value obtained by dividing the Z content by the total Z and Mn content can also be greater than 0.003 and less than 0.080.

[0062] In segregation 12, based on the atomic number, the value obtained by dividing the Mn content by the total Si and Mn content can also be greater than 0.02 and less than 0.50.

[0063] In segregation 12, based on the atomic number, the value obtained by dividing the Z content by the total Z and Ni content can also be greater than 0 and less than 0.060.

[0064] In segregation 12, the total content of Ca and Sr divided by the total content of Zr and Ti, based on the atomic number, can also be between 1.0 and 8.0.

[0065] When segregation 12 has a composition within the above-mentioned range, it is easy to further improve the high-temperature resistivity and reliability.

[0066] Furthermore, segregation 12 may also contain one or more oxides selected from Al, Mg, Li, B, and P. Containing one or more oxides selected from these elements readily improves temperature characteristics.

[0067] In addition, regarding segregation 12, when... Figure 2 In the case described, located in the dielectric layer, and as... Figure 3 and Figure 4 When the segregation 12 in the dielectric layer is in contact with or located within the inner electrode layer 3 as described, the Z content tends to be higher when comparing the Z content. The segregation 12 in the dielectric layer may contain Z in a proportion of 60% to 100% or 90% to 100%. The segregation 12 in contact with or located within the inner electrode layer 3 may also contain Z in a proportion of 0% to 50% or 0% to 20%.

[0068] The following is an explanation. Figure 1 An example of a method for manufacturing the multilayer ceramic capacitor 1 shown.

[0069] First, the manufacturing process of the component body 10 will be described. In the manufacturing process of the component body 10, dielectric paste that will become dielectric layer 2 after firing and internal electrode paste that will become internal electrode layer 3 after firing are prepared.

[0070] There are no particular limitations on the manufacturing method of the dielectric paste. For example, it can be manufactured by the following method: First, a raw material powder of the main component of the dielectric ceramic composition (hereinafter, sometimes referred to as the main component raw material powder) is prepared. As the raw material powder, commercially available perovskite compound powder may also be prepared. Alternatively, oxide powders of the A-site element and the B-site element of the perovskite compound may be prepared, dispersed in a solvent (e.g., pure water), dried, and heat-treated to prepare the raw material powder. There are no particular limitations on the holding temperature during the heat treatment for preparing the raw material powder. For example, it may be 900°C or higher and 1300°C or lower. There are no particular limitations on the holding time. For example, it may be 0.5 hours or higher and 5 hours or lower.

[0071] Alternatively, the oxide powder of the additive element can be simultaneously dispersed in a solvent together with the oxide powder of the A-site element and the oxide powder of the B-site element of the perovskite compound.

[0072] Alternatively, powders of compounds that have been sintered into oxides of each element, such as powders of carbonates of each element, can be used instead of the oxide powders of the elements mentioned above. Or, powders of composite compounds of each element can be used.

[0073] A portion of the oxide powder of the additive elements is added as a sintering aid containing at least MnCO3 and SiO2, and may also contain Al2O3. The sintering aid is prepared by pre-firing a mixed powder obtained by mixing the powders composed of the above-mentioned compounds. There is no particular limitation on the amount of sintering aid added, and it may be added at a rate of 1 to 5 parts by weight relative to 100 parts by weight of the perovskite compound powder.

[0074] Alternatively, the content of MnCO3 in the mixed powder before pre-firing can be 55% to 75% by weight, the content of Al2O3 can be 0% to 15% by weight, and the content of SiO2 can be 15% to 40% by weight. Pre-firing conditions can also include, for example, a firing temperature of 800°C to 1200°C and a holding time of 1 hour to 5 hours.

[0075] Next, the main component raw material powder and the raw material powder of Z oxide are mixed and pre-fired to obtain pre-fired powder. There are no particular restrictions on the pre-fired conditions, and the holding temperature can be set to 800℃~1200℃. The holding time can also be set to 1 hour~5 hours.

[0076] Next, the raw material powder, excluding the main component powder and the oxide powder of Z, is mixed with the pre-calcined powder described above, dispersed in pure water, dried, and further heat-treated to obtain dielectric powder. The holding temperature during heat treatment can be set to 100°C to 300°C. The holding time can be set to 0.5 hours to 5 hours.

[0077] By mixing the main component raw material powder and the raw material powder of Z oxide and pre-firing, a pre-fired powder is obtained, which readily contains Z oxide in the main phase particles. On the other hand, without producing the aforementioned pre-fired powder, Z oxide is readily contained in segregation. In particular, when the raw material powder of Z oxide is mixed with raw material powder other than the main component raw material powder, such as sintering aids, and pre-fired to obtain the pre-fired powder, the presence of Z oxide in segregation is especially likely. Therefore, by changing the proportion of Z oxide raw material powder in the pre-fired powder obtained by mixing and pre-firing with the main component raw material powder, Zm / Zs can be controlled.

[0078] The resulting dielectric powder, binder, and solvent (organic solvent or water) are then mixed to produce a dielectric paste. There are no particular restrictions on the types of binders and solvents. Alternatively, an organic carrier obtained by mixing the binder and organic solvent can be used instead of the binder and solvent. The dielectric paste may also contain additives such as plasticizers or dispersants as needed.

[0079] The internal electrode paste is obtained by mixing the above-mentioned conductive material raw materials, binders, and solvents (organic solvents or water). There are no particular restrictions on the types of binders and solvents. The internal electrode paste may also contain general-purpose materials or additives such as plasticizers, as needed.

[0080] Using the obtained pastes, green sheets and internal electrode patterns are formed, and they are stacked to obtain green chip blanks.

[0081] The obtained green die can also be debonded as needed. The debonding conditions can be set to well-known conditions; for example, the holding temperature can be set to 180°C to 400°C, and the holding time can be set to 0.5 hours to 24 hours. Furthermore, there are no particular restrictions on the atmosphere used during debonding. Alternatively, the holding temperature can be set to 1100°C or below under a reducing atmosphere.

[0082] After the binder removal process, the green chip is fired to obtain the device body 10. In this embodiment, the firing atmosphere can also be set to an oxygen partial pressure of 2.0 × 10⁻⁶. -13 above 1.0 × 10 -7A reducing atmosphere below atm. Other firing conditions can be set to well-known conditions, for example, the holding temperature can be set to 1200℃ to 1400℃ and the holding time can be set to 0.5 hours to 8 hours.

[0083] After firing, annealing can be performed as needed. There are no particular restrictions on the annealing conditions. For example, the holding temperature can be set between 500°C and 1150°C, and the holding time between 0.5 hours and 20 hours. The oxygen partial pressure in the annealing atmosphere can be set, for example, to 1.0 × 10⁻⁶. -9 3.0 × 10 atm or above -5 Below atm.

[0084] The dielectric ceramic composition constituting the dielectric layer 2 of the element body 10 obtained as described above is the aforementioned dielectric ceramic composition. If necessary, the element body 10 is subjected to end-face grinding, and an external electrode paste is applied and sintered to form an external electrode 4. Then, if necessary, a coating layer is formed on the surface of the external electrode 4 by plating or the like. There are no particular limitations on the method for preparing the external electrode paste; it can be prepared using the same method as the internal electrode paste.

[0085] Thus, the multilayer ceramic capacitor 1 of this embodiment is manufactured.

[0086] The embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments in any way, and various changes can be made without departing from the spirit of the present invention.

[0087] Example

[0088] The present invention will now be described with reference to more detailed embodiments, but the present invention is not limited to these embodiments.

[0089] Experimental Example 1

[0090] In Experiment 1, the following were prepared in the following order: Figure 1 The stacked ceramic capacitor 1 shown.

[0091] First, the dielectric paste was prepared.

[0092] A raw material powder containing a perovskite compound as the main component of the main phase particles (hereinafter, sometimes referred to as the main component raw material powder) was prepared. Specifically, raw material powders of Ca oxide, Sr oxide, Ba oxide, Zr oxide, Ti oxide, and Hf oxide were prepared and weighed in order to obtain a perovskite compound having the dielectric composition shown in Table 1. Furthermore, "γ oxide raw material powder" refers to powder of γ oxide and / or powder of a compound that has become a γ oxide through heat treatment. Then, each powder was dispersed in pure water, dried, and further heat-treated (at a temperature of 1150–1250°C for 0.5–5 hours), thereby preparing the main component raw material powder.

[0093] In addition, sintering aids were prepared. 65.5% by weight of MnCO3 powder and 34.5% by weight of SiO2 powder were mixed and pre-fired. The pre-fired conditions were set at a firing temperature of 1000℃ and a holding time of 2 hours.

[0094] In addition, powders of oxides of sintering aids and additive elements (raw material powders of Mn oxide, SiO2 powder, Ca oxide, Zr oxide, NiO powder, and / or Z(W) oxide) were prepared and weighed. In all embodiments, the content of the main component raw material powder was set to 100 parts by weight, containing 1 to 5 parts by weight of the above-mentioned sintering aid. However, when using 1 part by weight of sintering aid, if the content of either Mn or Si is too high, the amount of sintering aid used should be increased as much as possible within the range of less than 1 part by weight.

[0095] In the final dielectric ceramic composition, the addition amount of each raw material powder is controlled so that Zm / Zs is 3.5 to 5.0, Z / (Z+Si) in the segregation is 0.0035 to 0.0050, Z / (Z+Mn) in the segregation is 0.020 to 0.035, Mn / (Mn+Si) in the segregation is 0.20 to 0.35, Z / (Z+Ni) in the segregation is 0.020 to 0.030, and (Ca+Sr) / (Zr+Ti) in the segregation is 4.0 to 5.0. For example, in sample number 3, the content of the main component raw material powder is set to 100 parts by weight, such that the sintering aid is 2.0 parts by weight, the raw material powder of W oxide (WO3 powder) is 0.3 parts by weight, the raw material powder of Mn oxide (MnO powder) is 0.1 parts by weight, the raw material powder of SiO2 is 3.0 parts by weight, the raw material powder of Ca oxide (CaO powder) is 0.4 parts by weight, the raw material powder of Zr oxide (ZrO2 powder) is 0.1 parts by weight, and the raw material powder of NiO is 0.9 parts by weight.

[0096] In Experiment 1, the main component raw material powder and the raw material powder of oxide Z were mixed and pre-fired to obtain pre-fired powder. The pre-fired conditions were set at a holding temperature of 1000°C and a holding time of 2 hours. Furthermore, in Sample No. 7, only the main component raw material powder was mixed and pre-fired to obtain pre-fired powder.

[0097] Next, the raw material powders, excluding the main component powder and the oxide powder of Z, are mixed with the pre-calcined powder described above, dispersed in pure water, dried, and further heat-treated to obtain the dielectric powder. The holding temperature is set to 400°C, and the holding time is set to 2.0 hours.

[0098] As described above, the main component raw material powder and the raw material powder of the oxide of Z are mixed and pre-fired to obtain pre-fired powder. Then, the pre-fired powder is mixed with other raw materials such as sintering aids. This manufacturing method is designated as manufacturing method 1.

[0099] A dielectric paste was prepared by mixing dielectric powder and an organic carrier. For every 100 parts by weight of dielectric powder, 10 parts by weight of polyvinyl butyral resin, 5 parts by weight of dioctyl phthalate (DOP) as a plasticizer, and 100 parts by weight of ethanol as a solvent were mixed using a ball mill and pasted to obtain a dielectric layer paste.

[0100] The following describes the method for preparing the paste for internal electrodes. First, Ni powder, terpineol, ethyl cellulose, and benzotriazole were prepared in a mass ratio of 44.6:52.0:3.0:0.4. Then, they were pasted using a three-roll mill, thereby producing the paste for internal electrodes.

[0101] Next, using the aforementioned dielectric paste and internal electrode paste, a green chip was manufactured using a sheet fabrication method. Then, the green chip was subjected to a binder removal process, a firing process, and an annealing process to obtain a cuboid-shaped component body 10 with dimensions of 3.2 mm × 1.6 mm × 0.7 mm. Regarding the aforementioned dimensions, Figure 1 The horizontal dimension is 3.2mm. Figure 1 The longitudinal (layering direction) thickness is 0.7 mm. The holding temperature during firing is set to 1200–1300℃, the holding time to 2.0 hours, and the firing atmosphere to an oxygen partial pressure of 2.0 × 10⁻⁶. -13 above 1.0 × 10 -7 A reducing atmosphere below atm. In addition, in the obtained component body 10, the number of layers of dielectric layer 2 sandwiched by internal electrode layer 3 is set to 10, the average thickness of dielectric layer 2 sandwiched by internal electrode layer 3 is set to 5.0 μm, and the average thickness of internal electrode layer 3 is set to 1.2 μm.

[0102] Regarding the holding temperature during firing, preliminary tests were conducted on each sample at six holding temperatures: 1200℃, 1220℃, 1240℃, 1260℃, 1280℃, and 1300℃. Then, the lowest holding temperature among those used for densification of the component body 10 was employed. Whether the component body 10 was densified was confirmed by observing its cross-section using STEM. Specifically, the densification was achieved at 450 μm in the cross-section of the component body 10. 2 Within the field of view above, confirm whether the area of ​​the void portion is less than 2% of the area occupied by the dielectric layer 2 in the field of view.

[0103] Next, by forming a Cu-containing sintered electrode layer, a Ni-plated layer, and a Sn-plated layer on the outer surface of the aforementioned element body 10 in the order described, an external electrode 4 is formed, and a multilayer ceramic capacitor 1 is obtained.

[0104] (Composition of the dielectric ceramic composition)

[0105] Regarding the composition of the dielectric ceramic composition, the dielectric layer was analyzed using ICP-N (Inductively Coupled Phosphorescence) spectrophotometry. Then, it was confirmed that the dielectric composition and the proportions of the additive elements were substantially the same in both the feed composition and the dielectric ceramic composition.

[0106] (Zm / Zs and segregation composition)

[0107] The cross-section of the dielectric layer 2 contained in the multilayer ceramic capacitor 1 was observed using STEM-EDS. The magnification was set to 20,000x, and the observation range was set to 7μm × 7μm. Then, the main phase particles and segregation were distinguished.

[0108] Next, at least 10 measurement sites were set for the main phase particles contained in the observation range, and at least 10 measurement sites were set for the central part of segregation 12 contained in the observation range. STEM-EDS was used to perform point analysis on each measurement site to determine the composition of each measurement site. The content ratio of Z (Zm) was measured for all measurement sites contained in the main phase particles, and the average value of Zm was calculated. The content ratio of Z (Zs) was measured for all measurement sites contained in the segregation, and the average value of Zs was calculated. Then, Zm / Zs was calculated by dividing the average value of Zm by the average value of Zs. The results are shown in Table 1.

[0109] The contents of Z, Si, Mn, Ni, Ca, Sr, Zr, and Ti in all the measured fractions contained in the segregation were determined. Using the average values ​​of Z, Si, Mn, Ni, Ca, Sr, Zr, and Ti contents calculated from the obtained results, Z / (Z+Si), Z / (Z+Mn), Z / (Z+Ni), Mn / (Mn+Si), and (Ca+Sr) / (Zr+Ti) were calculated. The results are shown in Table 1.

[0110] (High-temperature resistivity test)

[0111] The insulation resistance of the multilayer ceramic capacitor 1 under high temperature and high electric field conditions was evaluated. Specifically, the insulation resistance was measured at 180°C when a DC voltage of 500V (100V / μm) was applied. The results are shown in Table 1. The insulation resistance under high temperature and high electric field conditions is 1.0 × 10⁻⁶. 12 For values ​​above Ω, it is considered to have good high-temperature resistivity.

[0112] (Reliability test)

[0113] The high-temperature load life of the multilayer ceramic capacitor 1 was evaluated. Specifically, the lifespan was measured at 200°C while maintaining an applied DC voltage of 800V (160V / μm). In this embodiment, the shorter of the time from the start of application to a decrease in insulation resistance by one decimal place, or the time from the start of application to sample failure, was defined as the lifespan. In this embodiment, the above evaluation was performed on 20 multilayer ceramic capacitors 1, and the mean time to failure (MTTF) was calculated based on the lifespan of each multilayer ceramic capacitor 1. The MTTF was set at 2.00 × 10⁻⁶. 2 More than 1.00 × 10 3 For hours, it is set to good reliability, with an MTTF of 1.00 × 10⁻⁶. 3For cases exceeding 1 hour, the reliability is set to exceptionally good. The results are shown in Table 1.

[0114] In Table 1, some of the experimental results are recorded as rE+s, which is r×10 s The meaning.

[0115] [Table 1]

[0116]

[0117] According to Table 1, samples 1-4, whose perovskite compound composition in the main phase particles is within the specified range and whose Zm is greater than Zs (Zm / Zs > 1.0), exhibit good high-temperature resistivity and reliability. Conversely, samples 5, 6, and 8, whose perovskite compound composition is outside the specified range, show decreased high-temperature resistivity and reliability. Sample 7, which does not contain Z, shows decreased high-temperature resistivity.

[0118] (Experimental Example 2)

[0119] Regarding sample number 3 of Experimental Example 1, 64.8% by weight of MnCO3 powder, 7.5% by weight of Al2O3 powder, and 27.7% by weight of SiO2 powder were mixed and pre-fired to obtain a sintering aid. Except for this, sample number 11 was carried out under the same conditions.

[0120] Starting with sample number 3 in Experimental Example 1, the main change was in the type of Z, and samples 12 through 19 were performed. In sample number 12, the ratio of W to Nb was 1:1 based on atomic number; in sample number 13, the ratio of W to Ta was 1:1 based on atomic number. In sample number 17, Mo was used to replace Z. In sample number 18, Y was used to replace Z. In sample number 19, Dy was used to replace Z. The results are shown in Table 2. The results of sample number 7, performed under the same conditions except that sample number 3 did not contain Z, are also recorded in Table 2.

[0121] [Table 2]

[0122]

[0123] According to Table 2, samples 11–16, whose composition of the perovskite compounds in the main phase particles is within the specified range and whose Zm is greater than Zs, exhibit good high-temperature resistivity and reliability. In contrast, samples 17–19, whose Z in sample 3 is replaced with an element other than Z, show reduced reliability. Sample 7, from which Z was removed in sample 3, shows reduced high-temperature resistivity.

[0124] (Experimental Example 3)

[0125] In sample number 21, the raw material powders of sintering aid and oxide of Z were mixed and pre-fired to obtain pre-fired powder. The pre-fired conditions were set at a temperature of 1000℃ and a holding time of 2 hours.

[0126] Next, the raw material powder, excluding the sintering aid and the oxide of Z, is mixed with the pre-calcined powder described above. These powders are then dispersed in pure water, dried, and further heat-treated to obtain the dielectric powder. The holding temperature is set to 400°C, and the holding time is set to 2 hours.

[0127] As described above, the raw material powders of sintering aid and oxide of Z are mixed and pre-calcined to obtain pre-calcined powder. The pre-calcined powder is then mixed with raw material powders other than the raw material powders of sintering aid and oxide of Z. This manufacturing method is designated as manufacturing method 2.

[0128] In sample number 22, the raw material powder of the main component and the raw material powder of the oxide of Z were mixed and pre-fired to obtain the first pre-fired powder. The pre-fired conditions were the same as those in preparation method 1. Separately, the raw material powder of the sintering aid and the oxide of Z were mixed and pre-fired to obtain the second pre-fired powder. The pre-fired conditions were the same as those in preparation method 2.

[0129] The raw material powder, excluding the main component raw material powder, sintering aid, and Z oxide raw material powder, is mixed with the first pre-calcined powder and the second pre-calcined powder mentioned above. These powders are then dispersed in pure water, dried, and further heat-treated to obtain dielectric powder. The holding temperature is set to 400°C, and the holding time is set to 2 hours. This manufacturing method is designated as Method 3.

[0130] In sample number 22, Zm = Zs. In sample number 23, Zm > Zs.

[0131] Samples 21 to 23 were performed in the same manner as sample 3, except that the method for manufacturing the dielectric powder was the same. The results are shown in Table 3.

[0132] [Table 3]

[0133]

[0134] According to Table 3, sample number 23, where the composition of the perovskite compound in the main phase particles is within the specified range and Zm is greater than Zs, exhibits good high-temperature resistivity and reliability. In contrast, the reliability of sample number 21, where the proportion of Z in the main phase particles is less than that in the segregation, and sample number 22, where the proportion of Z in the main phase particles is equal to that in the segregation, is reduced.

[0135] (Experimental Example 4)

[0136] For sample number 3, the amount of raw material powder of W oxide was mainly changed, thereby varying Zm / Zs within the range of 1.1 to 10. Samples 31 to 34 were performed. The results are shown in Table 4.

[0137] [Table 4]

[0138]

[0139] According to Table 4, when the composition of the perovskite compound contained in the main phase particles is within the specified range and Zm is greater than Zs, the high-temperature resistivity and reliability are good.

[0140] (Experimental Example 5)

[0141] For sample number 3, the composition of the sintering aid, the amount of sintering aid added, and / or the amount of SiO2 raw material powder added as an oxide powder of additive element were mainly changed, thereby changing Z / (Z+Si), and samples 41 to 44 were carried out. The results are shown in Table 5.

[0142] For sample number 3, the composition of the sintering aid, the amount of sintering aid added, and / or the amount of raw material powder of Mn oxide added as an additive element were mainly changed, thereby altering Z / (Z+Mn), and samples 51 to 54 were implemented. The results are shown in Table 6.

[0143] For sample number 3, the composition of the sintering aid, the amount of sintering aid added, and / or the amount of various raw material powders of Mn oxide added as an additive element were mainly changed, thereby changing Mn / (Mn+Si), and samples 61 to 64 were carried out. The results are shown in Table 7.

[0144] For sample number 3, the main change was in the amount of NiO raw material powder added, which altered Z / (Z+Ni), resulting in samples 71–75. In sample number 71, no NiO powder was added. The results are shown in Table 8.

[0145] For sample number 3, the amount of Zr oxide raw material powder added and / or the amount of Ca oxide raw material powder added were mainly changed, thereby changing (Ca + Sr) / (Zr + Ti), and samples 81 to 84 were carried out. The results are shown in Table 9.

[0146] [Table 5]

[0147]

[0148] [Table 6]

[0149]

[0150] [Table 7]

[0151]

[0152] [Table 8]

[0153]

[0154] [Table 9]

[0155]

[0156] According to Tables 5 to 9, even when the various parameters related to segregation are changed, the high-temperature resistivity and reliability are good when the composition of the perovskite compound contained in the main phase particles is within the specified range and Zm is greater than Zs.

Claims

1. A laminated ceramic electronic component, wherein, The stacked ceramic electronic component has a main body formed by stacking a dielectric layer and an internal electrode layer. The dielectric layer has main phase particles. The main body of the component has segregation. The main phase particles contain, on an atomic basis, the composition of the formula (Ca). 1-x-p Sr x Ba p ) m (Zr 1-y-z Ti y Hf z The perovskite compound represented by O3 is the main component. Satisfying 0 ≤ x ≤ 1.0, 0 ≤ p < 1.0, 0.9 ≤ m ≤ 1.1, 0 ≤ y ≤ 0.20, and 0 ≤ z < 1.0, The main phase particles also contain oxides of Z. Z is selected from one or more of V, Nb, Ta, and W. The segregation contains at least L, Mn, Si, and O. L is selected from one or more of Ca and Sr. The proportion of Z in the main phase particles is greater than the proportion of Z in the segregation.

2. The laminated ceramic electronic component according to claim 1, wherein, It satisfies 0≤x<0.80, 0≤p<0.40, 0.9<m<1.1, 0≤y≤0.10, and 0≤z<0.

20.

3. The laminated ceramic electronic component according to claim 1, wherein, It satisfies 0≤x<0.40, p=0, 0.9<m<1.1, 0.01<y≤0.10, and 0≤z<0.

20.

4. The laminated ceramic electronic component according to any one of claims 1 to 3, wherein, The proportion of Z contained in the main phase particles relative to the total content of all elements contained in the main phase particles, expressed on an atomic basis, is denoted as Zm. The proportion of Z contained in the segregation relative to the total content of all elements contained in the segregation is defined as Zs based on the number of atoms. 1.5 < Zm / Zs < 7.

5.

5. The laminated ceramic electronic component according to any one of claims 1 to 3, wherein, In the segregation, the value obtained by dividing the content of Z by the total content of Z and Si, based on the atomic number, is greater than 0.0002 and less than 0.0080.

6. The laminated ceramic electronic component according to any one of claims 1 to 3, wherein, In the segregation, the value obtained by dividing the content of Z by the total content of Z and Mn, based on the atomic number, is greater than 0.003 and less than 0.

080.

7. The laminated ceramic electronic component according to any one of claims 1 to 3, wherein, In the segregation, the Mn content divided by the total Si and Mn content, based on atomic number, is greater than 0.02 and less than 0.

50.

8. The laminated ceramic electronic component according to any one of claims 1 to 3, wherein, In the segregation, the value obtained by dividing the content of Z by the total content of Z and Ni, based on the atomic number, is greater than 0 and less than 0.

060.

9. The laminated ceramic electronic component according to any one of claims 1 to 3, wherein, In the segregation, the total content of Ca and Sr divided by the total content of Zr and Ti, based on the atomic number, is 1.0 or more and 8.0 or less.

10. The laminated ceramic electronic component according to any one of claims 1 to 3, wherein, The segregation contains one or more oxides selected from Al, Mg, Li, B and P.

11. The laminated ceramic electronic component according to any one of claims 1 to 3, wherein, The main component of the conductive material contained in the internal electrode layer is Ni or a Ni-based alloy.

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