Ceramic electronic component and manufacturing method thereof

Abstract

To provide a ceramic electronic component and a method of manufacturing the same capable of improving reliability.SOLUTION: A multilayer ceramic capacitor comprises a lamination structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately laminated. A main component of the dielectric layers is a ceramic having a perovskite structure at least containing Ba on an A site and having an A / B ratio of 0.980 or less. The internal electrode layers contain a common material. A total sum of molar ratios of Ti, Zr, and Hf among molar ratios of metal elements included in the common material is 90% or more, and that of Ba is 10% or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a ceramic electronic component and a method for manufacturing the same. [Background technology]

[0002] BACKGROUND ART In high frequency communication systems, such as mobile phones, ceramic electronic components such as multilayer ceramic capacitors are used to remove noise (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-095382 [Patent Document 2] Japanese Patent Application Publication No. 2019-134098 Summary of the Invention [Problem to be solved by the invention]

[0004] Mobile products and other applications require smaller, thinner, and higher-capacity ceramic electronic components. To meet these needs, it is necessary to provide internal electrode layers that maintain high continuity even when the layers are thin.

[0005] For example, by adding a common material to the internal electrode layer, the sintering temperature of the internal electrode layer can be increased, bringing it closer to the sintering temperature of the dielectric material of the dielectric layer, thereby increasing the continuity rate of the internal electrode layer and improving reliability. However, if a common material containing a large amount of Ba is used for a dielectric layer whose main component is a dielectric material having a perovskite structure that contains at least Ba (barium) in the A site and has an A / B ratio of 0.980 or less, the common material expelled from the internal electrode layer will diffuse into the dielectric material of the dielectric layer, causing abnormal grain growth and potentially resulting in insufficient reliability.

[0006] The present invention has been made in view of the above-mentioned problems, and has as its object to provide a ceramic electronic component that can improve reliability, and a method for manufacturing the same. [Means for solving the problem]

[0007] The ceramic electronic component according to the present invention has a laminated structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately laminated, and the dielectric layers are mainly composed of ceramics having a perovskite structure containing at least Ba in the A site and having an A / B ratio of 0.980 or less, and the internal electrode layers contain a common material, and the molar ratio of the metal elements contained in the common material is such that the sum of Ti, Zr, and Hf is 90% or more and Ba is 10% or less.

[0008] In the ceramic electronic component, the internal electrode layers may have a continuity ratio of 80% or more.

[0009] In the internal electrode layers of the ceramic electronic component, the ratio of the common material may be 5 mass % or more and 30 mass % or less.

[0010] In the ceramic electronic component, the common material may be TiO2, ZrO2 or HfO2.

[0011] The method for manufacturing a ceramic electronic component according to the present invention is characterized by comprising the steps of: obtaining a laminate by laminating a plurality of lamination units, on a dielectric green sheet of a dielectric material containing a ceramic material powder having a perovskite structure containing at least Ba in the A site and an A / B ratio of 0.980 or less, and printing a pattern of a metal conductive paste containing a co-material in which the molar ratio of the metal elements is Ti, Zr, and Hf in total 90% or more and Ba in total 10% or less, and firing the laminate.

[0012] In the metal conductive paste in the method for producing a ceramic electronic component, the ratio of the common material to the metal powder may be 5 mass % or more and 30 mass % or less.

[0013] In the method for manufacturing a ceramic electronic component, the common material may be TiO2, ZrO2 or HfO2. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a ceramic electronic component that can improve reliability and a method for manufacturing the same. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 2 is a partial cross-sectional perspective view of a multilayer ceramic capacitor. [Figure 2] FIG. 2 is a cross-sectional view taken along line AA in FIG. [Figure 3] FIG. 2 is a cross-sectional view taken along line BB in FIG. [Figure 4] This is the result of TMA of a Ni cylinder sample. [Figure 5] FIG. 10 is a diagram showing a continuity rate. [Figure 6] 1A to 1C are diagrams illustrating a flow of a method for manufacturing a multilayer ceramic capacitor. DETAILED DESCRIPTION OF THE INVENTION

[0016] Hereinafter, embodiments will be described with reference to the drawings.

[0017] (Embodiment) FIG. 1 is a partial cross-sectional perspective view of a multilayer ceramic capacitor 100 according to an embodiment. FIG. 2 is a cross-sectional view taken along line AA in FIG. 1. FIG. 3 is a cross-sectional view taken along line BB in FIG. 1. As illustrated in FIGS. 1 to 3, the multilayer ceramic capacitor 100 includes a laminated chip 10 having a substantially rectangular parallelepiped shape and external electrodes 20a, 20b provided on two opposing end faces of the laminated chip 10. Of the four faces of the laminated chip 10 other than the two end faces, the two faces other than the top and bottom faces in the stacking direction are referred to as side faces. The external electrodes 20a, 20b extend on the top, bottom and two side faces of the laminated chip 10 in the stacking direction. However, the external electrodes 20a, 20b are spaced apart from each other.

[0018] The multilayer chip 10 has a configuration in which dielectric layers 11 containing a ceramic material that functions as a dielectric and internal electrode layers 12 containing a base metal material are alternately stacked. The edges of each internal electrode layer 12 are alternately exposed at the end face of the multilayer chip 10 where the external electrode 20a is provided and the end face where the external electrode 20b is provided. As a result, each internal electrode layer 12 is alternately electrically connected to the external electrode 20a and the external electrode 20b. As a result, the multilayer ceramic capacitor 100 has a configuration in which multiple dielectric layers 11 are stacked with the internal electrode layers 12 interposed therebetween. In addition, in the laminate of the dielectric layers 11 and the internal electrode layers 12, the internal electrode layer 12 is arranged as the outermost layer in the stacking direction, and the upper and lower surfaces of the laminate are covered by cover layers 13. The cover layers 13 are primarily composed of a ceramic material. For example, the material of the cover layers 13 may have the same primary ceramic component as the dielectric layers 11.

[0019] The size of the multilayer ceramic capacitor 100 is, for example, 0.25 mm in length, 0.125 mm in width, and 0.125 mm in height, or 0.4 mm in length, 0.2 mm in width, and 0.2 mm in height, or 0.6 mm in length, 0.3 mm in width, and 0.3 mm in height, or 1.0 mm in length, 0.5 mm in width, and 0.5 mm in height, or 3.2 mm in length, 1.6 mm in width, and 1.6 mm in height, or 4.5 mm in length, 3.2 mm in width, and 2.5 mm in height, but is not limited to these sizes.

[0020] The internal electrode layers 12 are mainly composed of base metals such as Ni (nickel), Cu (copper), and Sn (tin). Noble metals such as Pt (platinum), Pd (palladium), Ag (silver), and Au (gold), or alloys containing these metals, may also be used as the internal electrode layers 12. The dielectric layers 11 are mainly composed of a ceramic material having a perovskite structure represented by the general formula ABO3, for example. Note that the perovskite structure is formed by an ABO3 that deviates from the stoichiometric composition. 3-α For example, the ceramic material contains at least Ba in the A site. For example, BaTiO3 (barium titanate) and Ba which forms a perovskite structure are used. 1-x-y Cax Sr y Ti 1-z Zr z O3 (0≦x≦1, 0≦y≦1, 0≦z≦1) etc. can be used.

[0021] The average thickness of each of the internal electrode layers 12 is, for example, 1.5 μm or less, 1.0 μm or less, or 0.7 μm or less. The average thickness of each of the dielectric layers 11 is, for example, 5.0 μm or less, 3.0 μm or less, or 1.0 μm or less.

[0022] 2, the region where the internal electrode layer 12 connected to the external electrode 20a and the internal electrode layer 12 connected to the external electrode 20b face each other is a region where capacitance is generated in the multilayer ceramic capacitor 100. Therefore, this region where capacitance is generated is referred to as a capacitance region 14. In other words, the capacitance region 14 is a region where adjacent internal electrode layers 12 connected to different external electrodes face each other.

[0023] The region where the internal electrode layers 12 connected to the external electrode 20a face each other without an internal electrode layer 12 connected to the external electrode 20b interposed therebetween is called the end margin 15. The region where the internal electrode layers 12 connected to the external electrode 20b face each other without an internal electrode layer 12 connected to the external electrode 20a interposed therebetween is also the end margin 15. In other words, the end margin 15 is the region where the internal electrode layers 12 connected to the same external electrode face each other without an internal electrode layer 12 connected to a different external electrode interposed therebetween. The end margin 15 is a region where no capacitance is generated.

[0024] 3, in the laminated chip 10, the regions extending from the two side surfaces of the laminated chip 10 to the internal electrode layers 12 are referred to as side margins 16. In other words, the side margins 16 are regions provided so as to cover the ends of the multiple internal electrode layers 12 stacked in the above-mentioned laminated structure, which extend to the two side surfaces. The side margins 16 are also regions that do not generate electrical capacitance.

[0025] In such a multilayer ceramic capacitor 100, if the continuity ratio of the internal electrode layers 12 decreases, electric field concentration occurs near the internal electrode layers 12 when a voltage is applied to the multilayer ceramic capacitor 100, which may reduce reliability. Therefore, there is a strong positive correlation between the continuity ratio of the internal electrode layers 12 and reliability. Factors that reduce the continuity ratio of the internal electrode layers 12 include different temperatures at which the materials sinter and shrink when firing the dielectric layers 11 and the internal electrode layers 12, and abnormal grain growth of the material of the dielectric layers 11. Here, abnormal grain growth can be defined as grain growth that exceeds five times the size of the blended main component ceramic particles, for example.

[0026] Therefore, in this embodiment, an A / B ratio (atomic concentration ratio between A-site elements and B-site elements) of 0.980 or less is used as the main component ceramic of the dielectric layer 11. This non-stoichiometric composition ratio can suppress grain growth of the dielectric layer 11.

[0027] In addition, by adding a common material to the internal electrode layer 12, the sintering temperature of the internal electrode layer 12 can be increased (sintering delay) and brought closer to the sintering temperature of the dielectric material of the dielectric layer 11, which can improve the continuity rate of the internal electrode layer 12. Part of this common material diffuses from the inside of the internal electrode layer 12 to the dielectric layer 11 during the sintering process of the internal electrode layer 12. Therefore, for example, it is considered that the common material has the same or similar composition as the dielectric layer 11.

[0028] For example, Patent Document 1 reports that by using barium titanate having an A / B ratio greater than 1 as a co-material, it is possible to suppress grain growth of the dielectric material of the dielectric layer 11 having an A / B ratio greater than 1, thereby improving reliability. However, if a co-material containing barium titanate containing a large amount of Ba as a main component is used for the dielectric layer 11 containing a main component ceramic having an A / B ratio of 0.980 or less, Ba diffused from the internal electrode layer 12 causes abnormal grain growth of the dielectric, the continuity rate of the internal electrode layer 12 decreases, and sufficient reliability cannot be obtained.

[0029] Therefore, in this embodiment, a common material is used in which the molar ratio of the contained metal elements is such that the total of Ti, Zr, and Hf is 90% or more and Ba is 10% or less. For example, TiO2, ZrO2, or HfO2 is used as the common material. This prevents or suppresses the diffusion of Ba into the dielectric layer 11, improving the continuity rate of the internal electrode layer 12 and improving reliability.

[0030] In this embodiment, the dielectric layer 11 is designed to have a non-stoichiometric composition with an A / B ratio of 0.980 or less for the main component ceramic, so that the grain growth behavior and characteristic fluctuations with respect to the A / B ratio of the main component ceramic of the dielectric layer 11 are gentle. Even if TiO2, ZrO2, or HfO2 diffuses from the internal electrode layer 12, Ti, Zr, and Hf are homologous elements (group 4) and can have a tetravalent valence, so they are likely to form a solid solution in the B site of the main component ceramic of the dielectric layer 11, no significant change in characteristics occurs, and abnormal grain growth is suppressed.

[0031] If a typical A-rich (A / B ratio > 1) dielectric material is used as the main ceramic component of the dielectric layer 11, TiO2, ZrO2, or HfO2 may diffuse into the dielectric layer 11, causing abnormal grain growth and reducing reliability.

[0032] ​From the above, it is only by using a common material in which the A / B ratio of the main component ceramic of the dielectric layer 11 is 0.980 or less and the molar ratio of the contained metal elements is such that the total of Ti, Zr, and Hf is 90% or more and Ba is 10% or less that the continuity rate of the internal electrode layer 12 can be improved and the reliability of the multilayer ceramic capacitor 100 can be improved.

[0033] In Patent Document 2, the IR characteristics and high temperature load life are improved by using a common material with a higher Zr concentration than the main component ceramic of the dielectric layer 11. The main component of the common material is BaTi 1-z Zr z O3, and is a common material containing Ba based on the premise of a BaTiO3-based perovskite compound. Therefore, the technology of Patent Document 2 differs from the common material according to this embodiment in both composition and mechanism of action. For example, in this embodiment, a dielectric material with an A / B ratio of 0.980 or less is used as the main component ceramic of the dielectric layer 11, and the diffusion of Ba from the internal electrode layer 12 is suppressed, and the reaction between Ba and the Ti, Zr or Hf-rich shell phase is suppressed, thereby suppressing abnormal grain growth in the vicinity of the internal electrode layer 12. Therefore, the less Ba in the common material, the more desirable it is, and BaTi with a high Zr concentration is preferable. 1-z Zr z It is fundamentally different from the O3 co-material.

[0034] Figure 4 shows the results of thermomechanical analysis (TMA) of a Ni cylindrical sample. The sample was prepared by adding TiO2, ZrO2, etc. to Ni paste, drying it, then adding a binder, granulating it, and pressing it into a cylindrical shape. The addition of TiO2 or ZrO2 delayed sintering compared to samples without the co-material. Furthermore, when comparing TiO2 and ZrO2 at the same amount, ZrO2 delayed sintering more. Hf is also a homologous element of Zr, and HfO2 has nearly identical chemical properties to ZrO2, so it is likely to similarly delay sintering. This indicates that TiO2, ZrO2, and HfO2 function as co-materials that inhibit sintering of the metal material contained in the internal electrode layer 12. However, as mentioned above, these co-materials cause abnormal grain growth in typical dielectric materials with an A / B ratio > 0.980, making them unsuitable as co-materials and therefore not used. They are useful as co-materials when used with dielectric materials with an A / B ratio ≤ 0.980 as described in this embodiment to fabricate multilayer ceramic capacitors.

[0035] If the amount of the co-material added to the internal electrode layer 12 is small, there is a risk that the sintering temperature cannot be raised sufficiently. Therefore, it is preferable to set a lower limit to the amount of the co-material added to the internal electrode layer 12. For example, in the internal electrode layer 12, the amount of the co-material added is preferably 5 mass% or more, more preferably 7.5 mass% or more, and further preferably 10 mass% or more.

[0036] If the amount of the co-material added to the internal electrode layer 12 is large, the conductivity may decrease, and the function as an electrode may be impaired. Therefore, it is preferable to set an upper limit to the amount of the co-material added to the internal electrode layer 12. For example, in the internal electrode layer 12, the amount of the co-material added is preferably 30 mass% or less, more preferably 25 mass% or less, and further preferably 20 mass% or less.

[0037] It is preferable to use TiO2, ZrO2, or HfO2 as the common material in the internal electrode layer 12, but these may be used in combination. In this case, the molar ratio of the contained metal elements should be such that the total of Ti, Zr, and Hf is 90% or more and Ba is 10% or less. For example, ceramics containing Ba, such as BaTiO3, may also be contained.

[0038] For example, the internal electrode layer 12 preferably has a continuity rate of 80% or more. Fig. 5 is a diagram showing the continuity rate. As illustrated in Fig. 5, in an observation area of length L0 in a certain internal electrode layer 12, the lengths L1, L2, ..., Ln of the metal parts are measured and summed, and the ratio of the metal parts, ΣLn / L0, can be defined as the continuity rate of that layer. The continuity rate of the internal electrode layer 12 is more preferably 85% or more, and even more preferably 90% or more.

[0039] From the viewpoint of suppressing grain growth of the dielectric layer 11, the A / B ratio of the main component ceramic of the dielectric layer 11 is preferably 0.98 or less, and more preferably 0.96 or less. From the viewpoint of the dielectric constant, the A / B ratio of the main component ceramic of the dielectric layer 11 is preferably 0.90 or more, and more preferably 0.94 or more.

[0040] Alternatively, the main component ceramic of the dielectric layer 11 may be based on barium titanate and may contain at least one of ZrO2 and HfO2 as a solid solution. In this case, the main component ceramic of the dielectric layer 11 may have a core-shell structure with a core mainly composed of barium titanate and a shell made of a diffusion layer rich in Ti, Zr, or Hf.

[0041] Next, a description will be given of a method for manufacturing the multilayer ceramic capacitor 100. FIG.

[0042] (raw powder production process) First, a dielectric material for forming the dielectric layer 11 is prepared. The A-site and B-site elements contained in the dielectric layer 11 are typically present in the form of a sintered compact of ABO particles. For example, BaTiO3 is a tetragonal compound with a perovskite structure and exhibits a high dielectric constant. BaTiO3 is generally obtained by synthesizing barium titanate by reacting a titanium source such as titanium dioxide with a barium source such as barium carbonate. Each material is weighed so that the A / B ratio in the resulting perovskite structure is 0.980 or less. Various methods are known for synthesizing the ceramic that is the main component of the dielectric layer 11, including the solid-state method, the sol-gel method, and the hydrothermal method. Any of these methods can be used in this embodiment.

[0043] The resulting ceramic powder is then mixed with a specific additive compound depending on the intended purpose. Examples of additive compounds include oxides of Zr, Mg, Mn, V (vanadium), Cr (chromium), and Eu, as well as oxides or glasses of Co (cobalt), Ni, Li (lithium), B (boron), Na (sodium), K (potassium), and Si (silicon). If necessary, oxides of rare earth elements other than Eu (Sc (scandium), Y, La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Pm (promethium), Sm (samarium), Gd (gadolinium), Tb (terbium), Dy, Ho, Er (erbium), Tm (thulium), Yb (ytterbium), and Lu (lutetium)) may also be added.

[0044] For example, a ceramic material is prepared by wet-mixing a ceramic raw material powder with a compound containing an additive compound, followed by drying and pulverization. For example, the ceramic material obtained as described above may be pulverized as necessary to adjust the particle size, or may be combined with a classification process to adjust the particle size. A dielectric material is obtained by the above process.

[0045] (Lamination process) Next, a binder such as polyvinyl butyral (PVB) resin, an organic solvent such as ethanol or toluene, and a plasticizer are added to the obtained dielectric material and wet mixed. Using the obtained slurry, a strip-shaped dielectric green sheet having a thickness of, for example, 0.5 μm or more is coated on a substrate by, for example, a die coater method or a doctor blade method, and then dried.

[0046] Next, a metal conductive paste containing an organic binder for forming internal electrodes is printed on the surface of the dielectric green sheet by screen printing, gravure printing, etc., to form an internal electrode layer pattern that alternately leads to a pair of external electrodes with different polarities. The metal conductive paste contains a co-material whose molar ratio of metal elements is 90% or more in total of Ti, Zr, and Hf, and 10% or less of Ba.

[0047] Thereafter, the dielectric green sheets on which the internal electrode layer patterns are printed are punched out to a predetermined size, and the punched dielectric green sheets are stacked, with the base material peeled off, by a predetermined number of layers (for example, 100 to 1000 layers) so that the internal electrode layers 12 and the dielectric layers 11 alternate, and so that the edges of the internal electrode layers 12 are alternately exposed at both longitudinal end faces of the dielectric layers 11 and are alternately drawn out to a pair of external electrodes 20a, 20b of opposite polarity. Cover sheets for forming cover layers 13 are pressure-bonded to the top and bottom of the stacked dielectric green sheets, and the sheets are cut to a predetermined chip size (for example, 1.0 mm × 0.5 mm).

[0048] (Firing process) The ceramic laminate thus obtained was subjected to binder removal treatment in an N2 atmosphere, and then a metal paste that would become the base layer of the external electrodes 20a, 20b was applied by dipping. -12 ~10 -9 The mixture is then fired in a reducing atmosphere at 1100 to 1300° C. for 10 minutes to 2 hours at 1 atm. In this way, the multilayer ceramic capacitor 100 is obtained.

[0049] (Reoxidation treatment process) Thereafter, a re-oxidation treatment may be performed at 600°C to 1000°C in an N2 gas atmosphere.

[0050] (Plating process) Thereafter, the underlying layers of the external electrodes 20a, 20b are plated with a metal coating of Cu, Ni, Sn, etc. Through the above steps, the multilayer ceramic capacitor 100 is completed.

[0051] According to the manufacturing method of this embodiment, the A / B ratio of the main component ceramic of the dielectric material is 0.980 or less, and a common material is used in which, among the molar ratios of the contained metal elements, the total of Ti, Zr, and Hf is 90% or more and Ba is 10% or less, so that the continuity rate of the internal electrode layer 12 is improved and the reliability of the multilayer ceramic capacitor 100 is improved.

[0052] If the amount of co-material added to the metal conductive paste of the internal electrode layer pattern is small, the sintering temperature may not be raised sufficiently. Therefore, it is preferable to set a lower limit for the amount of co-material added to the metal conductive paste. For example, the amount of co-material added to the metal conductive paste is preferably 5 mass% or more, more preferably 7.5 mass% or more, and even more preferably 10 mass% or more.

[0053] If the amount of co-material added to the metal conductive paste of the internal electrode layer pattern is large, the conductivity may decrease and the function as an electrode may be impaired. Therefore, it is preferable to set an upper limit on the amount of co-material added to the metal conductive paste. For example, in the metal conductive paste, the amount of co-material added is preferably 30 mass% or less, more preferably 25 mass% or less, and even more preferably 20 mass% or less.

[0054] It is preferable to use TiO2, ZrO2, or HfO2 as the co-material in the metal conductive paste, but these may also be used in combination. In this case, the molar ratio of the contained metal elements should be such that the total of Ti, Zr, and Hf is 90% or more and Ba is 10% or less. For example, ceramics containing Ba, such as BaTiO3, may also be included.

[0055] From the viewpoint of suppressing grain growth of the dielectric layer 11, the A / B ratio of the main component ceramic of the dielectric material is preferably 0.98 or less, more preferably 0.96 or less. From the viewpoint of the dielectric constant, the A / B ratio of the main component ceramic of the dielectric layer material is preferably 0.90 or more, more preferably 0.94 or more.

[0056] In the above embodiments, a multilayer ceramic capacitor has been described as an example of a ceramic electronic component, but the present invention is not limited to this. For example, other electronic components such as a varistor or a thermistor may also be used. [Example]

[0057] The multilayer ceramic capacitor according to the embodiment was fabricated and its characteristics were examined.

[0058] Example 1 Barium titanate with an A / B ratio of 0.960, various additives, and organic solvent were weighed out to a specified ratio, and mixed and crushed with 0.5 mm zirconia beads to obtain a dielectric material. After dispersion, the slurry was measured using a particle size distribution measuring device, and all samples were found to be approximately 100 nm. A 2.5 μm dielectric green sheet was coated with the slurry obtained by adding a binder, and a Ni paste kneaded with each co-material was printed on it. ZrO2 was used as the co-material. The amount of co-material added was 10 parts by weight relative to Ni. The amount of Ni paste applied was approximately 3 μg / mm 2 Ten dielectric green sheets printed with Ni paste were stacked, and cover sheets were placed on top and bottom, pressed together, and then cut to the desired shape. The resulting laminate was debindered in an N2 atmosphere, after which a metal conductive paste primarily composed of Ni was applied as a base layer from both end faces to each side of the laminate and dried. The laminate was then fired in a reducing atmosphere to obtain a sintered body.

[0059] Example 2 In Example 2, ZrO2 was used as the co-material. The amount of the co-material added was 5 parts by weight relative to Ni. Other conditions were the same as in Example 1.

[0060] Example 3 In Example 3, TiO2 was used as the co-material. The amount of the co-material added was 10 parts by weight relative to Ni. Other conditions were the same as in Example 1.

[0061] Example 4 In Example 4, TiO2 was used as the co-material. The amount of the co-material added was 5 parts by weight relative to Ni. Other conditions were the same as in Example 1.

[0062] Example 5 In Example 5, the A / B ratio of the dielectric material barium titanate was set to 0.980. ZrO2 was used as the co-material. The amount of the co-material added was 10 parts by weight relative to Ni. Other conditions were the same as in Example 1.

[0063] Example 6 In Example 6, the A / B ratio of the dielectric material barium titanate was set to 0.940. ZrO2 was used as the co-material. The amount of the co-material added was 10 parts by weight relative to Ni. Other conditions were the same as in Example 1.

[0064] (Comparative Example 1) In Comparative Example 1, no co-material was added to the metal conductive paste for forming the internal electrode layers. The other conditions were the same as in Example 1.

[0065] (Comparative Example 2) In Comparative Example 2, BaTiO3 was used as the common material. The amount of the common material added was 10 parts by weight relative to Ni. Other conditions were the same as in Example 1.

[0066] (Comparative Example 3) In Comparative Example 3, BaCO3 was used as the co-material. The amount of the co-material added was 10 parts by weight relative to Ni. Other conditions were the same as in Example 1.

[0067] Comparative Example 4 In Comparative Example 4, the A / B ratio of the barium titanate of the dielectric material was set to 1.010. The other conditions were the same as in Example 1.

[0068] (Comparative Example 5) In Comparative Example 5, the A / B ratio of the barium titanate of the dielectric material was set to 0.990. Other conditions were the same as those of Comparative Example 2.

[0069] (Comparative Example 6) In Comparative Example 6, the A / B ratio of the barium titanate of the dielectric material was set to 0.990. The other conditions were the same as those of Example 1.

[0070] The capacitance of each multilayer ceramic capacitor in Examples 1 to 6 and Comparative Examples 1 to 6 was measured using an LCR meter. The continuity ratio of the internal electrode layers was calculated using image analysis software by polishing the resin-embedded samples and observing them with a laser microscope. The continuity ratio of the internal electrode layers was calculated by dividing the length of the connected internal electrode layers on the polished surface by the length of the internal electrode layers, including the disconnected portions. Furthermore, the dielectric particles of the resin-embedded samples were observed using an SEM. Samples in which some of the dielectric particles had grown to more than five times the size of the blended barium titanate particles were judged to have abnormal grain growth. HALT (accelerated life test) was evaluated by applying a voltage of 50 V per 1 μm of dielectric layer thickness after firing at 125°C. Samples with an average HALT life of 3,000 min or more were rated as passing (good). Elements contained in the common materials were quantified by EDS analysis using SEM, TEM, etc. The results are shown in Table 1. [Table 1]

[0071] Comparative Example 1 was judged as a failure (×). This is thought to be because the continuity ratio decreased due to the absence of a co-material. Comparative Example 2 was judged as a failure (×). This is thought to be because the addition of BaTiO3 as a co-material caused a large amount of Ba to diffuse into the dielectric layer, resulting in abnormal grain growth and a decrease in the continuity ratio. Comparative Example 3 was judged as a failure (×). This is thought to be because the addition of BaCO3 as a co-material caused a large amount of Ba to diffuse into the dielectric layer, resulting in abnormal grain growth and a decrease in the continuity ratio. Comparative Example 4 was judged as a failure (×). This is thought to be because the A / B ratio of the dielectric material exceeded 0.980, resulting in abnormal grain growth and a decrease in the continuity ratio. Comparative Example 5 was judged as a failure (×). This is thought to be because the addition of BaTiO3 as a co-material caused a large amount of Ba to diffuse into the dielectric layer, resulting in abnormal grain growth and a decrease in the continuity ratio. Furthermore, it is believed that the A / B ratio of the dielectric material exceeded 0.980, which caused abnormal grain growth and reduced the continuity ratio. Comparative Example 6 was judged as a failure "x". This is believed to be because the A / B ratio of the dielectric material exceeded 0.980, which caused abnormal grain growth and reduced the continuity ratio.

[0072] In contrast, all of Examples 1 to 6 were judged to be passable with a "Good" grade. This is thought to be because the ceramic with an A / B ratio of 0.980 or less was used as the main component ceramic of the dielectric material, and the common material of the internal electrode layer was one in which the molar ratio of the contained metal elements was such that the total of Ti, Zr, and Hf was 90% or more and Ba was 10% or less.

[0073] Although the embodiments of the present invention have been described in detail above, the present invention is not limited to such specific embodiments, and various modifications and variations are possible within the scope of the gist of the present invention as defined in the claims. [Explanation of symbols]

[0074] 10 stacked chips 11 Dielectric layer 12 Internal electrode layer 13 Cover Layer 14 Capacity area 15 End Margin 16 Side Margin 20a,20b external electrode 100 Multilayer ceramic capacitors

Claims

1. The laminated structure has a plurality of dielectric layers and a plurality of internal electrode layers alternately laminated, the dielectric layer is mainly composed of a ceramic having a perovskite structure containing at least Ba in the A site and an A / B ratio of 0.940 or more and 0.980 or less; The internal electrode layer contains 5 mass% or more and 10 mass% or less of a common material, A ceramic electronic component, characterized in that, of the molar ratios of metal elements contained in the common material, the total of Ti, Zr, and Hf is 90% or more, and Ba is 10% or less.

2. 2. The ceramic electronic component according to claim 1, wherein the internal electrode layers have a continuity ratio of 80% or more.

3. The ceramic electronic component according to claim 1, wherein the common material contains HfO 2 .

4. The co-material is TiO ２ , ZrO ２ or HfO ２ 3. The ceramic electronic component according to claim 1, wherein:

5. a step of obtaining a laminate by laminating a plurality of lamination units, on which a pattern of a metal conductive paste containing 5 mass% or more and 10 mass% or less of a co-material, the co-material having a molar ratio of Ti, Zr, and Hf of 90% or more and Ba of 10% or less, is printed, on a dielectric green sheet of a dielectric material containing a ceramic material powder having a perovskite structure containing at least Ba in the A site and an A / B ratio of 0.940 or more and 0.980 or less; and firing the laminate.

6. The method for manufacturing a ceramic electronic component according to claim 5, wherein the common material contains HfO 2 .

7. The co-material is TiO ２ , ZrO ２ or HfO ２ 6. The method for producing a ceramic electronic component according to claim 5, wherein

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