Laminated ceramic electronic component and method for manufacturing same

Abstract

The present invention provides a laminated ceramic electronic component capable of suppressing diffusion of copper of an external electrode into an internal electrode, and a method for manufacturing the same. The laminated ceramic electronic component includes: a main body in which internal electrodes having nickel as a main component and dielectric layers having ceramic as a main component are alternately laminated in a first direction, the main body having a pair of end surfaces facing each other in a second direction, the internal electrodes being alternately exposed to the pair of end surfaces; and a pair of external electrodes that are in contact with the exposed internal electrodes and have copper as the main component, the molar ratio of copper to nickel of the first internal electrode in an end edge region is greater than the molar ratio of copper to nickel of the first internal electrode in the capacitance region, and the end edge region is an end portion of the main body in the second direction when viewed from the first direction. The capacitor region is a central portion in the second direction when viewed from the first direction, and the first and second internal electrodes overlap each other.

Description

Technical Field

[0001] This invention relates to laminated ceramic electronic components and their manufacturing methods. Background Technology

[0002] It is known that in multilayer ceramic electronic components such as multilayer ceramic capacitors having an internal electrode mainly composed of nickel and an external electrode mainly composed of copper, the molar ratio of copper in the internal electrode on the main surface side is higher than the copper concentration in the internal electrode in the central part (for example, Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2021-15925 Summary of the Invention

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

[0007] When copper from the external electrode diffuses into the internal electrode, and copper reacts with nickel, the internal electrode expands, sometimes causing cracks in the substrate.

[0008] The present invention was made in view of the above-mentioned technical problems, and its purpose is to provide a multilayer ceramic electronic component and a method thereof capable of suppressing the diffusion of copper from the external electrode to the internal electrode.

[0009] Technical solutions for solving technical problems

[0010] The present invention is a laminated ceramic electronic component comprising: a body wherein a plurality of internal electrodes, primarily composed of nickel, and a plurality of dielectric layers, primarily composed of ceramic, are alternately laminated in a first direction; the body having a pair of end faces facing each other in a second direction, wherein the laminated plurality of internal electrodes are alternately exposed on the pair of end faces; and a pair of external electrodes respectively contacting the plurality of internal electrodes exposed from the pair of end faces, wherein the layers of the pair of external electrodes in contact with the plurality of internal electrodes are primarily composed of copper; wherein the molar ratio of copper to nickel of the first internal electrode in the end edge region is greater than the molar ratio of copper to nickel of the first internal electrode in the capacitance region; the end edge region is the end of the body in the second direction when viewed from the first direction, and includes the first internal electrode of one of the plurality of internal electrodes exposed on the pair of end faces but excludes the second internal electrode of the other of the pair of end faces; and the capacitance region is the central portion of the body in the second direction when viewed from the first direction, wherein the first internal electrode and the second internal electrode overlap each other in the region.

[0011] In the above structure, the copper-to-nickel molar ratio of the outermost internal electrode in the first direction is greater than that of the copper-to-nickel molar ratio of the internal electrode in the central part in the first direction within the capacitor region.

[0012] In the above structure, the copper-to-nickel molar ratio at the end of the internal electrode in the third direction, which is substantially orthogonal to the first and second directions, is greater than the copper-to-nickel molar ratio at the center of the internal electrode in the third direction.

[0013] This invention relates to a method for manufacturing a laminated ceramic electronic component, comprising: a step of preparing a body in which a plurality of internal electrodes, primarily composed of nickel, and a plurality of dielectric layers, primarily composed of ceramic, are alternately laminated in a first direction; the body having a pair of end faces facing each other in a second direction; the laminated plurality of internal electrodes being alternately exposed on the pair of end faces; the molar ratio of copper to nickel of the first internal electrode in the end edge region being greater than the molar ratio of copper to nickel of the first internal electrode in the capacitance region; the end edge region being the end of the body in the second direction when viewed from the first direction, and including the first internal electrode of one of the plurality of internal electrodes exposed on the pair of end faces but excluding the second internal electrode of the other of the pair of end faces; the capacitance region being the central portion of the body in the second direction when viewed from the first direction, and in which the first internal electrode and the second internal electrode overlap each other; and a step of forming a pair of external electrodes, wherein the pair of external electrodes are respectively in contact with the plurality of internal electrodes exposed from the pair of end faces, and the layers of the pair of external electrodes in contact with the plurality of internal electrodes are primarily composed of copper.

[0014] In the above structure, the process of forming the pair of external electrodes may include: applying a metal paste in a manner that contacts each of the plurality of internal electrodes exposed from the pair of end faces; and sintering the applied metal paste.

[0015] The above structure can be configured such that the process of preparing the main body includes: a process of preparing a laminate, wherein the molar ratio of copper to the main component metal element of the ceramic in the dielectric pattern disposed in the end edge region of the laminate in such a way as to contact the second internal electrode in the second direction is greater than the molar ratio of copper to the main component metal element of the ceramic in the green sheet overlapping the first internal electrode and the second internal electrode in the first direction; and a process of firing the laminate.

[0016] In the above structure, before the process of forming the external electrode, in the capacitor region, the molar ratio of copper to nickel of the outermost internal electrode in the first direction is greater than the molar ratio of copper to nickel of the internal electrode in the central part in the first direction.

[0017] In the above structure, before the process of forming the external electrode, in the capacitor region, the molar ratio of copper to nickel at the end of the internal electrode in the third direction, which is substantially orthogonal to the first direction and the second direction, is greater than the molar ratio of copper to nickel at the center of the internal electrode in the third direction.

[0018] Invention Effects

[0019] According to the present invention, a multilayer ceramic electronic component capable of suppressing the diffusion of copper from an external electrode to an internal electrode and a method thereof are provided. Attached Figure Description

[0020] Figure 1 This is a partial cross-sectional perspective view of the stacked ceramic capacitor according to the embodiment.

[0021] Figure 2 yes Figure 1 AA-line cross-section diagram.

[0022] Figure 3 yes Figure 1 BB line cross-section diagram.

[0023] Figure 4 yes Figure 1 CC line cross-section diagram.

[0024] Figure 5 yes Figure 1 DD line cross-section diagram.

[0025] Figure 6 This is a flowchart illustrating a method for manufacturing a multilayer ceramic capacitor according to an embodiment.

[0026] Figure 7 (a) is a plan view showing a method for manufacturing a multilayer ceramic capacitor according to an embodiment. Figure 7 (b) is Figure 7 (a) AA line cross section diagram.

[0027] Figure 8 This is a cross-sectional view showing a method for manufacturing a multilayer ceramic capacitor according to an embodiment.

[0028] Figure 9 This is a cross-sectional view showing a method for manufacturing a multilayer ceramic capacitor according to an embodiment.

[0029] Figure 10 (a) and Figure 10 (b) is a cross-sectional view showing the manufacturing method of the multilayer ceramic capacitor according to the embodiment.

[0030] Figure 11 This is a cross-sectional view of a multilayer ceramic capacitor used as a comparison object.

[0031] Figure 12 This is a cross-sectional view of a multilayer ceramic capacitor used as a comparison object.

[0032] Figure 13 (a) to Figure 13 (b) is a schematic diagram showing the molar ratio of copper in the internal electrodes.

[0033] Figure 14 (a) to Figure 14 (b) is a schematic diagram showing the molar ratio of copper in the internal electrodes.

[0034] Explanation of reference numerals in the attached figures

[0035] 10 main bodies

[0036] Internal electrodes of 12a and 12b

[0037] 13a Part 1

[0038] 13b Part Two

[0039] 14 Dielectric layer

[0040] 16a, 16b covering dielectric layers

[0041] 18a and 18b side dielectric layers

[0042] 20a, 20b External Electrodes

[0043] 30, 31 raw slices

[0044] 32 Metal Patterns

[0045] 33 Dielectric Pattern

[0046] 34, 34a, and 35-layer laminates

[0047] 51 and 52 end faces

[0048] 53, 54 Side View

[0049] 55 Lower surface

[0050] 56. Upper surface

[0051] 61x, 61y Central Department

[0052] 60 Capacitor Area

[0053] 63, 65 end

[0054] 64 edge regions

[0055] 66 Side edge region

[0056] The range is 80 to 89. Detailed Implementation

[0057] Hereinafter, with reference to the accompanying drawings, an embodiment will be described using a multilayer ceramic capacitor as an example of a multilayer ceramic electronic component.

[0058] (Implementation Method)

[0059] Figure 1 This is a partial cross-sectional perspective view of the stacked ceramic capacitor 100 according to the embodiment. Figure 2 yes Figure 1 AA-line cross-section diagram. Figure 3 yes Figure 1 BB line cross-section diagram. Figure 4 yes Figure 1 CC line cross-section diagram. Figure 5 yes Figure 1 DD line cross-sectional view. In Figures 2 to 5 In the diagram, the first part 13a of the internal electrodes 12a and 12b is represented by a shading line with one type of parallel line, and the second part 13b is represented by a shading line with two types of parallel lines intersecting.

[0060] exist Figures 1 to 5 In this diagram, the Z direction (first direction) is the stacking direction of the stacked dielectric layer 14 and internal electrodes 12a and 12b, and is the direction in which the lower surface 55 and upper surface 56 of the main body 10 are opposite to each other. The X direction (second direction) is the length direction of the main body 10, and is the direction in which a pair of end faces 51 and 52 of the main body 10 are opposite to each other. The Y direction (third direction) is the width direction of the main body 10 and internal electrodes 12a and 12b, and is the direction in which a pair of side faces 53 and 54 of the main body 10 are opposite to each other. The X, Y, and Z directions are approximately orthogonal to each other.

[0061] The multilayer ceramic capacitor 100 includes a body 10 having a generally rectangular parallelepiped shape and external electrodes 20a and 20b. The body 10 includes a multilayer 11 and side dielectric layers 18a and 18b disposed on both sides of the multilayer 11 in the Y direction.

[0062] The laminate 11 has multiple dielectric layers 14, multiple internal electrodes 12a and 12b, and covering dielectric layers 16a and 16b. The multiple internal electrodes 12a and 12b are stacked alternately. Internal electrodes 12a are led out to one end face 51, and internal electrodes 12b are led out to another end face 52. One of the multiple dielectric layers 14 is disposed between one of the multiple internal electrodes 12a and one of the multiple internal electrodes 12b. The outermost layers of the laminate 11 in the stacking direction (Z direction) are the internal electrodes 12a and 12b, and the lower and upper surfaces of the laminate 11 are covered by covering dielectric layers 16a and 16b, respectively. Furthermore, the internal electrodes 12a and 12b are examples of first and second internal electrodes.

[0063] The regions of internal electrodes 12a and 12b are divided into a first part 13a and a second part 13b. The copper concentration in the second part 13b is higher than that in the first part 13a. The copper concentration is expressed as the molar ratio of copper to nickel, the main component metal element of the internal electrodes 12a and 12b. This is sometimes abbreviated as the copper molar ratio.

[0064] Internal electrodes 12a and 12b are alternately exposed on end faces 51 and 52. Internal electrode 12a is exposed from end face 51, but internal electrode 12b is not exposed from end face 51. Internal electrode 12b is exposed from end face 52, but internal electrode 12a is not exposed from end face 52. That is, internal electrodes 12a and 12b are connected to different end faces 51 and 52, respectively.

[0065] like Figure 2 and Figure 4 As shown, capacitor region 60 is the central portion 62 in the X and Y directions of the main body 10 when viewed from the Z direction, and the internal electrodes 12a and 12b overlap each other. End edge region 64 is the end portion of the main body 10 that is adjacent to both sides of the central portion 62 in the X direction when viewed from the Z direction, and contains only one of the internal electrodes 12a or 12b.

[0066] For example, one end edge region 64 includes an internal electrode (first internal electrode) 12a but does not include an internal electrode (second internal electrode) 12b. The other end edge region 64 includes an internal electrode (first internal electrode) 12b but does not include an internal electrode (second internal electrode) 12a. Within each end edge region 64, there is a lead-out region for the internal electrode 12a relative to end face 51 and a lead-out region for the internal electrode 12b relative to end face 52.

[0067] Furthermore, in the Z direction, the uppermost internal electrode 12a and the lowermost internal electrode 12b each lack the first portion 13a, and only have the second portion 13b. Among the other internal electrodes 12a and 12b, the region within the end edge region 64 is the second portion 13b, the region within the end 63 on the side of the end edge region 64 within the capacitor region 60 is the second portion 13b, and the region within the central portion 61x sandwiched between the two ends 63 in the X direction is the first portion 13a.

[0068] like Figure 3 As shown, the side edge region 66 is the end of the main body 10 in the Y direction and is not provided with internal electrodes 12a and 12b. The side edge region 66 is formed by side dielectric layers 18a and 18b. Among each of the internal electrodes 12a and 12b other than the uppermost internal electrode 12a and the lowermost internal electrode 12b in the Z direction, the region within the end 65 on the side edge region 66 side of the capacitor region 60 in the Y direction is the second part 13b, and the region within the central part 61y sandwiched between the ends 65 in the Y direction is the first part 13a.

[0069] like Figure 2 , Figure 4 and Figure 5 As shown, in the internal electrodes 12a and 12b, the portion existing within the end edge region 64 of the main body 10 is entirely the second portion 13b.

[0070] As described above, the capacitor region 60 includes second portions 13b of internal electrodes 12a and 12b at both ends in the X, Y, and Z directions, and first portions 13a of internal electrodes 12a and 12b at the center in the X, Y, and Z directions. That is, the second portions 13b of internal electrodes 12a and 12b are provided on the surface of the capacitor region 60, and the first portions 13a of internal electrodes 12a and 12b are provided inside the capacitor region 60.

[0071] External electrode 20a contacts internal electrode 12a exposed from body 10 at end face 51. External electrode 20b contacts internal electrode 12b exposed from body 10 at end face 52. External electrode 20a covers end face 51, and also covers the ends of sides 53 and 54, lower surface 55, and upper surface 56 in the -X direction. External electrode 20b contacts internal electrode 12b at end face 51. External electrode 20b covers end face 52, and also covers the ends of sides 53 and 54, lower surface 55, and upper surface 56 in the +X direction.

[0072] The dimensions of the multilayer ceramic capacitor 100 are, for example, 0.25 mm in length (length in the X direction), 0.125 mm in width (width in the Y direction), and 0.125 mm in height (height in the Z direction); 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 are not limited to these dimensions.

[0073] The thickness of the side dielectric layers 18a and 18b is, for example, 10 μm to 30 μm. The length of the end edge region 64 in the X direction is, for example, 10 μm to 50 μm.

[0074] The internal electrodes 12a and 12b are primarily composed of nickel (Ni). The thickness of the internal electrodes 12a and 12b is, for example, between 0.1 μm and 1 μm.

[0075] The dielectric layer 14 is, for example, a ceramic material having a perovskite structure represented by the general formula ABO3 as the main phase. This perovskite structure contains ABO3, which deviates from its stoichiometric composition. 3-α For example, as this ceramic material, barium titanate (BaTiO3), calcium zirconate (CaZrO3), calcium titanate (CaTiO3), strontium titanate (SrTiO3), magnesium titanate (MgTiO3), and Ba, which forms a perovskite structure, can be used. 1-x-y Ca x Sr y Ti 1-z Zr z Choose at least one of the following: O3 (0≤x≤1, 0≤y≤1, 0≤z≤1), etc. Ba 1-x- y Ca x Sr y Ti 1-z Zr z O3 is barium strontium titanate, barium calcium titanate, barium zirconate, barium zirconate titanate, calcium zirconate titanate, and barium calcium zirconate titanate, etc. For example, in the dielectric layer 14, the main component ceramic contains 90 at% or more. The thickness of the dielectric layer 14 is, for example, 0.3 μm or more and 2 μm or less.

[0076] Additives may be added to the dielectric layer 14. Examples of additives to the dielectric layer 14 include oxides of zirconium (Zr), hafnium (Hf), magnesium (Mg), manganese (Mn), molybdenum (Mo), vanadium (V), chromium (Cr), rare earth elements (yttrium (Y), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), and ytterbium (Yb)), or oxides containing cobalt (Co), nickel (Ni), lithium (Li), boron (B), sodium (Na), potassium (K), or silicon (Si), or glasses containing cobalt, nickel, lithium, boron, sodium, potassium, or silicon.

[0077] The composition of the main component ceramic covering dielectric layers 16a, 16b and side dielectric layers 18a, 18b can be the same as or different from the main component ceramic of dielectric layer 14.

[0078] The layer (base metal layer 22) of the external electrodes 20a and 20b that is in contact with at least the internal electrodes 12a and 12b is primarily composed of copper (Cu) and includes a glass component for densifying the external electrodes 20a and 20b, and a ceramic component such as a co-material for controlling the sinterability of the external electrodes 20a and 20b. The glass component is an oxide of barium (Ba), lithium (Sr), calcium (Ca), zinc, aluminum, silicon, or boron. The co-material is, for example, a ceramic component with the same main component as the dielectric layer 14. Furthermore, a coating primarily composed of base metals such as nickel, copper, or tin may be formed on the surface of the external electrodes 20a and 20b. Additionally, a film of conductive resin such as epoxy resin or polyurethane resin may be formed on the surface of the coating.

[0079] (Manufacturing method of multilayer ceramic capacitors)

[0080] The manufacturing method of the multilayer ceramic capacitor 100 is described. Figure 6 This is a flowchart illustrating a method for manufacturing a multilayer ceramic capacitor according to an embodiment.

[0081] (Raw chip forming process)

[0082] First, green sheet 30 is formed (step S10). In step S10, a dielectric material is prepared, for example, by adding various additive compounds (sintering aids, etc.) to ceramic powder. A binder such as polyvinyl butyral (PVB) resin, an organic solvent such as ethanol or toluene, and a plasticizer are added to the prepared dielectric material and wet-mixed to generate a slurry. Using the generated slurry, green sheet 30 is coated onto a substrate using, for example, a die-coating machine or a doctor blade method. The substrate is, for example, a coated (polyethylene terephthalate) film. Then, green sheet 30 is dried.

[0083] Similarly, a green wafer 31 is formed for covering dielectric layers 16a and 16b and side dielectric layers 18a and 18b. Copper or a copper compound is added to the dielectric material used for the green wafer 31. The copper compound is, for example, copper oxide (CuO or CuO2). As a result, the copper concentration of the green wafer 31 is higher than that of the green wafer 30.

[0084] (Pattern forming process)

[0085] Next, a metal pattern 32 and a dielectric pattern 33 are formed on the green sheet 30 or 31 (step S12). Figure 7 (a) is a top view showing a method for manufacturing a multilayer ceramic capacitor according to an embodiment. Figure 7 (b) is Figure 7 (a) AA line cross section diagram. Figure 7 (a) and Figure 7 The cutting line 36 in (b) is the cutting line that cuts the laminate 35 in process S18.

[0086] In step S12, firstly, a metal paste comprising nickel powder, an organic binder, and an organic solvent is prepared. The metal paste may contain ceramic particles as a co-material without the addition of copper. Figure 7 (a) and Figure 7 As shown in (b), a metallic pattern 32 is formed by printing a metallic paste onto a raw film 30 using, for example, gravure printing.

[0087] Next, a dielectric paste comprising ceramic powder, copper powder or copper compound powder, organic binder, organic solvent, and plasticizer is prepared. The copper compound is, for example, copper oxide (CuO or CuO2). The dielectric paste is printed on the green film 30 using, for example, gravure printing to form a dielectric pattern 33. The dielectric pattern 33 is the inverse pattern of the metal pattern 32, preferably with almost no gap between the dielectric pattern 33 and the metal pattern 32.

[0088] Thus, a laminate 34 is formed on the green sheet 30 having a metal pattern 32 and a dielectric pattern 33. On the green sheet 31 used to cover the dielectric layer 16a, a laminate 34a is also formed on the green sheet 31 by forming a metal pattern 32 and a dielectric pattern 33.

[0089] (Layering process)

[0090] Next, the green wafer 31 and the laminated wafer 34a are stacked (step S14). Figure 8 This is a cross-sectional view showing a method for manufacturing a multilayer ceramic capacitor according to an embodiment, equivalent to... Figure 7The AA section of (a). In process S14, multiple laminated sheets 34 are laminated on laminated sheet 34a, and finally a green sheet 31 for covering dielectric layer 16b is laminated. Thus, a laminated sheet 35 with laminated sheet 34a and multiple laminated sheets 34 is formed. At this time, the metal pattern 32 is staggered in the X direction with each layer offset.

[0091] (Crimping process)

[0092] Next, the laminate 35 is crimped (step S16). In step S16, multiple laminates 34a and 34 are crimped together by applying pressure to the laminate 35 formed in step S14. As a crimping method, hydrostatic pressure crimping can be used, for example.

[0093] (Cutting process)

[0094] Next, the laminate 35 is cut (step S18). In step S18, the laminate 35 is cut along the specified cutting line 36 in the lamination direction using a cutting blade, thereby preparing a plurality of laminates 11. Figure 9 This is a cross-sectional view showing a method for manufacturing a multilayer ceramic capacitor according to an embodiment, equivalent to... Figures 1-5 The BB line cross-section. For example... Figure 9 As shown, in the laminate 11, the internal electrodes 12a and 12b are exposed from the sides 53a and 54a.

[0095] (Paste the lateral shoot)

[0096] Next, the green sheet is attached (step S20). In step S20, the green sheet 31 used for the side dielectric layer 18a is pressed against the side surface 53a of the laminate 11 to attach the green sheet 31 to the side surface 53a. Similarly, the green sheet 31 is attached to the side surface 54a of the laminate 11. After step S22, the main body 10 can also be ground by methods such as tumbling. As a result, the corners of the main body 10 are chamfered.

[0097] (Firing process)

[0098] Next, the laminate 11 with green sheets 31 attached to sides 53a and 54a is fired (step S22). In step S22, the laminate 11 with the attached green sheets 31 is subjected to a binder removal treatment in a nitrogen atmosphere at 250°C to 500°C, and then fired in a reducing atmosphere at 1300°C to 1400°C. This sintersects the individual particles within the laminate 11 and the green sheets 31. During the binder removal treatment at a lower temperature than the firing treatment, copper in the green sheets 31 and the dielectric pattern 33 diffuses into the metal pattern 32. If the green sheets 31 and the dielectric pattern 33 contain copper in the form of copper oxide, the copper oxide is reduced and diffuses into the internal electrodes 12a and 12b. To reduce the copper oxide, hydrogen can also be included in the binder removal treatment atmosphere. Figures 2-4 The molar ratio of copper in the second portion 13b increases. On the other hand, copper does not diffuse into the first portion 13a to the same extent as it diffuses into the second portion 13b, and the molar ratio of copper in the first portion 13a is smaller than that in the second portion 13b. Through the debinder treatment, the copper in the green sheet 31 and the dielectric pattern 33 substantially moves to the second portion 13b.

[0099] During the debinding process, copper mainly diffuses into the second part 13b. Therefore, during the firing process, the copper in the green sheet 31 and the dielectric pattern 33 reacts with the nickel near the surface of the internal electrodes 12a and 12b, which can suppress the expansion of the internal electrodes 12a and 12b.

[0100] (External electrode formation process)

[0101] Next, external electrodes 20a and 20b are formed (step S24). Step S24 includes steps S24a to S24c. Figure 10 (a) and Figure 10 (b) is a cross-sectional view showing the manufacturing method of the multilayer ceramic capacitor according to the embodiment, showing the... Figure 2 The same cross-section. In step S24a, a metal paste comprising copper powder, an organic binder, and an organic solvent is prepared. The metal paste may contain ceramic particles as a co-material. For example... Figure 10 As shown in (a), metal paste is applied, for example, by dipping, to the entire end face 51 of the body 10, as well as to the ends of the sides 53, 54, lower surface 55 and upper surface 56 on the end face 51 side.

[0102] Next, in step S24b, the metal paste is sintered in a nitrogen atmosphere at a temperature of 750°C to 850°C, which is lower than the firing temperature in step S22. As a result, the metal paste is sintered onto the body 10, forming a base metal layer 22. At this time, copper diffuses from the base metal layer 22 into the body 10, but because copper is pre-contained in the second portion 13b of the internal electrodes 12a and 12b, the diffusion of copper is suppressed.

[0103] In process S24c, such as Figure 10 As shown in (b), a plating layer 24 is formed on the base metal layer 22 by performing a plating process. The plating layer 24 is, for example, a layer mainly composed of copper, a layer mainly composed of nickel, and a layer mainly composed of tin, starting from the base metal layer 22 side. External electrodes 20a and 20b are formed by the base metal layer 22 and the plating layer 24.

[0104] (Laminated ceramic capacitors used as a comparison object)

[0105] Figure 11 This is a cross-sectional view of the multilayer ceramic capacitor 110 used as a comparison object, equivalent to... Figure 12 AA line cross section. Figure 12 This is a cross-sectional view of the multilayer ceramic capacitor 110 used as a comparison object, equivalent to... Figure 11 The BB cross section. The multilayer ceramic capacitor 110, used as a comparison object, is in... Figure 6 In steps S10 and S12, copper is not added to the green sheet 31 and dielectric pattern 33, which is different from the manufacturing method of the multilayer ceramic capacitor 100 in the embodiment.

[0106] Figure 13 (a) to Figure 14 (b) is a schematic diagram showing the molar ratio of copper in the internal electrodes. Figure 13 (a) and Figure 13 (b) means Figure 6 A diagram showing the molar ratio of copper in the internal electrode 12a of the main body 10 after process S22 and before process S24. Figure 14 (a) and Figure 14 (b) is a graph showing the molar ratio of copper in the internal electrode 12a of the main body 10 after process S24. Figure 13 (a) and Figure 14 (a) indicates the molar ratio of copper at the position in the X direction within the internal electrode 12a. Line 75 indicates the comparison object. Figure 11 The "75" indicates the molar ratio of copper in the internal electrode 12a between the arrows. Lines 75a and 75b indicate the embodiment. Figure 2 The molar ratio of copper in the internal electrode 12a between the arrows, indicated by "75a" and "75b" respectively.

[0107] Figure 13 (b) and Figure 14 (b) indicates the molar ratio of copper at the Y-direction position within internal electrode 12a. Line 76 indicates the comparison object. Figure 12 The molar ratio of copper in the internal electrode 12a between the arrows indicated by "76". Lines 76a and 76b indicate the embodiment. Figure 5The molar ratio of copper in the internal electrode 12a between the arrows, indicated by "76a" and "76b" respectively.

[0108] In the multilayer ceramic capacitor 110 used as a comparison object, no copper is added to the green sheet 31 and the dielectric pattern 33. Therefore, as Figure 13 (a) and Figure 13 As shown in lines 75 and 76 of (b), after the firing process in step S22, the internal electrode 12a does not contain copper in substance.

[0109] In addition, in the process S24 of sintering the base metal layer 22, such as Figure 14 (a) and Figure 14 As shown in lines 75 and 76 of (b), copper in the metal paste that forms the base metal layer 22 diffuses into the inner electrode 12a and reacts with nickel (see reference). Figure 11 (Arrow 70). As a result, the molar ratio of copper in the end edge region 64 increases. At this time, the molar ratio of copper in the end face 51 of the end edge region 64 is the largest, and the molar ratio of copper decreases as it moves closer to the center 62 from the end face 51 in the X direction.

[0110] In the edge region 64, if the diffused copper reacts with the nickel of the internal electrode 12a, the internal electrode 12a expands, as... Figure 11 and Figure 12 As indicated by arrow 72, stress is applied in the direction of expansion towards the end edge region 64. Therefore, as Figure 11 and Figure 12 As shown, crack 74 is generated at the corner of the main body 10.

[0111] On the other hand, in the implementation method, in Figure 6 In processes S10 and S12, the green sheet 31 and the dielectric pattern 33 contain copper. Therefore, in the debinder treatment of process S22, the copper in the green sheet 31 and the dielectric pattern 33 mainly diffuses into the second portion 13b within the internal electrodes 12a and 12b. This is the inventor's insight; for example, if copper oxides such as CuO2 and CuO are added to the green sheet 30, which is mainly composed of barium titanate, and a debinder treatment is performed, the copper diffuses into the internal electrodes 12a and 12b.

[0112] In one example, in green sheet 31, when the molar ratio of CuO2 to BaTiO3 is 2 mol%, the molar ratio of copper to nickel in the internal electrodes 12a and 12b in contact with green sheet 31 is 4 mol%, and the molar ratio of copper to nickel in the internal electrodes 12a and 12b not in contact with green sheet 31 is 2 mol%. Alternatively, in green sheet 31, when the molar ratio of CuO2 to BaTiO3 is 5 mol%, the molar ratio of copper to nickel in the internal electrodes 12a and 12b in contact with green sheet 31 is 9.1 mol%, and the molar ratio of copper to nickel in the internal electrodes 12a and 12b not in contact with green sheet 31 is 4.7 mol.

[0113] In the main body 10 before the firing process (process S22), the green sheet 31 of the capacitor region 60 contains almost no copper. Therefore, during the firing process, in the internal electrode 12a near the center in the Z direction, copper hardly diffuses into the region within the central portion 61x of the capacitor region 60 in the X direction.

[0114] Therefore, as Figure 13 As shown by line 75a in (a), the internal electrode 12a within the central portion 61x contains almost no copper. On the other hand, the dielectric pattern 33 contains copper before the firing process, so during the firing process, copper diffuses from the dielectric pattern 33 to the internal electrode 12a within the end edge region 64.

[0115] Therefore, as Figure 13 As shown by line 75a in (a), the molar ratio of copper in the internal electrode 12a within the edge region 64 is greater than that in the internal electrode 12a within the central portion 61x. Furthermore, during the firing process, copper also diffuses from the dielectric pattern 33 to the internal electrode 12a within the end 63 of the central portion 62 where the capacitor region 60 exists. Therefore, as... Figure 13 As shown by line 75a in (a), the molar ratio of copper in the internal electrode 12a within the end 63 is greater than that in the internal electrode 12a within the central portion 61x, and is substantially the same as that in the internal electrode 12a within the end edge region 64.

[0116] Before the firing process, the green sheet 31, which forms the dielectric layers 16a and 16b, contains copper. Therefore, during the firing process, copper diffuses from the green sheet 31, which forms the dielectric layers 16a and 16b, towards the uppermost (or lowermost) internal electrode 12a (12b) in the Z direction. Thus, as... Figure 13 As shown in (a), in the central portion 61x of the laminate 11 in the X direction, the molar ratio of copper in the uppermost internal electrode 12a (line 75b) is greater than the molar ratio of copper in the internal electrode 12a near the center (line 75a).

[0117] Furthermore, during the firing process, within the edge region 64, copper diffuses from the green sheet 31 and the dielectric pattern 33 towards the uppermost internal electrode 12a in the Z direction. Therefore, as... Figure 13 As shown in (a), in the end edge region 64 and the end 63, the molar ratio of copper in the uppermost internal electrode 12a (line 75b) is greater than the molar ratio of copper in the internal electrode 12a near the center (line 75a).

[0118] Before the firing process, the green sheet 31, which becomes the side dielectric layers 18a and 18b, contains copper. Therefore, during the firing process, copper diffuses from the green sheet 31, which becomes the side dielectric layers 18a and 18b, to the internal electrodes 12a and 12b in the Y-direction end 65 of the capacitor region 60.

[0119] like Figure 13 As shown in (b), regarding the internal electrode 12a near the center in the Z direction, the molar ratio of copper in the internal electrode 12a within the end 65 in the Y direction is greater than the molar ratio of copper in the internal electrode 12a within the central portion 61y in the Y direction (line 76a). Furthermore, as... Figure 13 As shown in (b), in the central portion 61y in the Y direction, the molar ratio of copper in the uppermost internal electrode 12a in the Z direction (line 76b) is greater than the molar ratio of copper in the internal electrode 12a near the center in the Z direction (line 76a). In the end portion 65 in the Y direction, the molar ratio of copper in the uppermost internal electrode 12a (line 76b) is also greater than the molar ratio of copper in the internal electrode 12a near the center in the Z direction (line 76a).

[0120] In summary, the molar ratio of copper after the sintering process increases in the following order from 80 to 83b.

[0121] Range 80 (copper molar ratio: 2.0): In the internal electrodes 12a and 12b near the center in the Z direction, the first portion 13a exists within the central portion 61x in the X direction.

[0122] Range 81a (copper molar ratio: 4.0): the second portion 13b, located within the end edge region 64 and the central portion 61y in the Y direction, in the inner electrodes 12a and 12b near the center in the Z direction.

[0123] Range 81b (copper molar ratio: 4.2): the second portion 13b, located within the end edge region 64 and the end portion 65 in the Y direction, in the inner electrodes 12a and 12b near the center in the Z direction.

[0124] Range 82 (molar ratio of copper: 4.6): In the inner electrodes 12a and 12b at the uppermost or lowermost part in the Z direction, the second part 13b exists within the central part 61x in the X direction.

[0125] Range 83a (molar ratio of copper: 4.8): The second portion 13b, located within the end edge region 64 and the central portion 61y in the Y direction, in the uppermost or lowermost internal electrodes 12a and 12b in the Z direction.

[0126] Range 83b (copper molar ratio: 5.0): The second portion 13b, located within the end edge region 64 and the end portion 65 in the X direction, in the uppermost or lowermost internal electrodes 12a and 12b in the Z direction.

[0127] In process S24, when forming the base metal layer 22, the internal electrodes 12a and 12b within the end edge region 64 contain copper. Therefore, in the multilayer ceramic capacitor 100 of this embodiment, the molar ratio of copper between the base metal layer 22 and the internal electrodes 12a and 12b is greater than that in the multilayer ceramic capacitor 110 used as a comparison object. Therefore, during the sintering process S24b of the base metal layer 22, the diffusion of copper from the base metal layer 22 to the internal electrodes 12a and 12b is suppressed, and the reaction between copper and nickel is also suppressed.

[0128] If Figure 14 The lines 75, 75a and 75b in (a) are respectively with Figure 13 Comparing lines 75, 75a, and 75b in (a), it can be seen that in the multilayer ceramic capacitors 100 and 110, copper diffusion of the base metal layer 22 occurs in the region Xdf in the X direction from the end face 51 to the end edge region 64. Here, the amount of copper increase in the end edge region 64 of the multilayer ceramic capacitor 100 of the embodiment is less than that of the multilayer ceramic capacitor 110 used as a comparison. Therefore, in this embodiment, the reaction between copper and nickel is suppressed. Figure 11 and Figure 12 The stress, as shown by arrow 72, is suppressed, and the formation of crack 74 is suppressed.

[0129] like Figure 13 As shown in lines 75a and 75b of (a), before process S24, in the end edge region 64, the molar ratio of copper in the uppermost internal electrode 12a in the Z direction is greater than the molar ratio of copper in the internal electrode 12a near the center in the Z direction. Therefore, in the uppermost internal electrode 12a, compared with the internal electrode 12a near the center, the diffusion of copper from the base metal layer 22 is further suppressed, and the reaction of copper with nickel is further suppressed.

[0130] If Figure 14 Lines 75a and 75b in (a) are respectively with Figure 13Comparing lines 75a and 75b in (a), it can be seen that in the end-edge region 64, the increase in molar ratio caused by the diffusion of copper towards the uppermost internal electrode 12a is less than the increase in molar ratio caused by the diffusion of copper towards the central internal electrode 12a. Furthermore, the diffusion of copper remains within the end-edge region 64, and copper does not substantially diffuse into the central portion 62 where the capacitor region 60 exists. Additionally, as... Figure 14 As shown by lines 76, 76a, and 76b in (b), near end face 51, the molar ratios of copper in the uppermost internal electrode 12a, the central internal electrode 12a, and the internal electrode 12a of the multilayer ceramic capacitor used as a comparison are substantially equal. This is because the base metal layer 22 contains more copper as its main component than the amount diffused into the internal electrodes 12a and 12b.

[0131] In summary, the molar ratio of copper after the formation of the external electrode in process S24 increases in the following order: 85 to 89.

[0132] Range 85 (molar ratio of copper: 2.0): In the internal electrodes 12a and 12b near the center in the Z direction, the first portion 13a exists within the central portion 61x in the X direction.

[0133] Range 86 (copper molar ratio: 4.0): the second portion 13b present in the inner electrodes 12a and 12b near the center in the Z direction, within the end 63 in the X direction and in the end edge region 64 on the side of the end 63.

[0134] Range 87 (molar ratio of copper: 4.6): In the uppermost or lowermost internal electrodes 12a and 12b in the Z direction, the second part 13b exists within the central part 61x in the X direction.

[0135] Range 88 (copper molar ratio: 4.8): The second portion 13b of the end edge region 64 located within and to the side of the end 63 in the X direction, within or at the uppermost or lowermost internal electrodes 12a and 12b in the Z direction.

[0136] Range 89 (molar ratio of copper: 22): In the internal electrodes 12a and 12b, a second portion 13b exists near the end face 51 within the end edge region 64.

[0137] As described above, compared to the comparative multilayer ceramic capacitor 110, in the edge region 64, copper is less likely to diffuse from the base metal layer 22 (metal paste) to the regions 86 and 88 of the internal electrode 12a, thus suppressing the reaction between copper and nickel and inhibiting the expansion of the internal electrodes 12a and 12b. Therefore, as Figure 11 and Figure 12The formation of such cracks 74 was further suppressed.

[0138] According to the implementation method, before step S24, such as Figure 13 As shown in (a), the molar ratio of copper in range 81a is greater than that in range 80. Therefore, after step S24b of sintering the metal paste, as... Figure 14 As shown in (a), the increase in the molar ratio of copper in the end edge region 64 caused by copper diffusion from the metal paste (lines 75a and 75b) is reduced compared to the increase in the molar ratio of copper in the case of the multilayer ceramic capacitor 110 (line 75). That is, in the multilayer ceramic capacitor 100 according to the embodiment, the amount of copper diffusion from the base metal layer 22 to the inner electrodes 12a and 12b after firing is reduced compared to the multilayer ceramic capacitor 110. Therefore, the reaction between copper and nickel can be suppressed, and the formation of cracks and the like can be suppressed. In addition, if copper oxide is retained in the covering dielectric layers 16a and 16b, the side dielectric layers 18a and 18b, and the end edge region 64, their respective density is increased, the strength of the body 10 is increased, and the moisture resistance is improved.

[0139] The molar ratio of copper in raw sheets 30, 31, and dielectric pattern 33 is, for example, the molar ratio of copper relative to the main component metal element of the ceramic. If the main component of the ceramic is barium titanate, the main component metal element is titanium or barium. If there are multiple main component elements, the most easily detectable metal element can be used as the reference.

[0140] In processes S10 and S12, the molar ratio of copper in the green sheet 31 and the dielectric pattern 33 to the main component metal element of the ceramic is preferably 0.1 mol% to 10 mol%. Therefore, before the external electrode formation process S24, the molar ratio of copper to nickel in range 81 is, for example, 0.1 mol% to 20 mol%, and the molar ratio of copper to nickel in range 80 is, for example, 0 mol% to 10 mol%. For example, if the main component of the ceramic in the green sheet 31 and the dielectric pattern 33 is barium titanate, and CuO2 is added as a copper compound, the molar ratio of copper to titanium in the green sheet 31 and the dielectric pattern 33 is 1 mol% to 10 mol%. At this time, the molar ratio of copper to nickel in range 81 is, for example, 1 mol% to 10 mol%, and the molar ratio of copper to nickel in range 80 is 0 mol% to 5 mol%.

[0141] After step S24, the molar ratio of copper to nickel in range 86 is greater than that in range 85. The molar ratio of copper to nickel in range 85 is the molar ratio of copper to nickel in the central portion 61x of capacitor region 60. The molar ratio of copper to nickel in range 86 is, for example, 1 to 7, and the molar ratio of copper to nickel in range 85 is, for example, 0.5 to 4.0. The molar ratio of copper to nickel in range 86 is preferably, for example, 1.2 times or more, more preferably 1.5 times or more, and even more preferably 2 times or more than that in range 85. If the nickel contains copper, the resistance becomes high. The smaller molar ratio of copper in range 85 within the internal electrodes 12a and 12b of capacitor region 60 reduces the resistance of the internal electrodes 12a and 12b, thus improving the characteristics of the capacitor.

[0142] As a means Figure 13 The method in which the molar ratio of copper in range 81a is greater than the molar ratio of copper in range 80, is in Figure 7 (a) and Figure 7 In (b), when forming the laminate 34, the molar ratio of copper in ranges 80 and 81 within the metal pattern 32 can be made to a desired value. However, it is difficult to change the molar ratio of copper within the same metal pattern 32.

[0143] Therefore, as Figure 7 (a) to Figure 8 As explained, in the prepared laminate 35, the molar ratio of copper to the main component metal element of the ceramic in the dielectric pattern 33 disposed in the end edge region 64 in a manner contacting the internal electrodes 12a and 12b in the X direction is greater than the molar ratio of copper to the main component metal element of the ceramic in the green sheet 30 overlapping with the internal electrodes 12a and 12b in the Z direction. In step S22, the laminate 35 is fired. This allows for simple... Figure 13 The molar ratio of copper in range 81a of (a) is greater than the molar ratio of copper in range 80.

[0144] Additionally, before process S24, such as Figure 13 As shown in (b), the molar ratio of copper to nickel in range 83a is higher than that in range 81a. The molar ratio of copper to nickel in range 83a is, for example, 1.5 to 7.5. Consequently, in the end edge region 64, in the second portion 13b of the uppermost or lowermost internal electrodes 12a and 12b, compared to the second portion 13b of the internal electrodes 12a and 12b near the center, the reaction between copper and nickel is suppressed, and the expansion of the internal electrodes 12a and 12b is suppressed. Therefore, the formation of crack 74 can be further suppressed. The molar ratio of copper in range 88 is preferably, for example, 1.2 times or more, and more preferably 1.5 times or more, the molar ratio of copper in range 86.

[0145] As a method to make the molar ratio of copper in the range 82 greater than that in the range 80, in Figure 7 (a) and Figure 7 In (b), copper is added to the green sheet 31 that forms the dielectric layers 16a and 16b. In this manufacturing process, as... Figure 14 As shown in (a), the molar ratio of copper to nickel in the range 87 of the outermost inner electrodes 12a and 12b in the Z direction is greater than the molar ratio of copper to nickel in the range 85 of the inner electrodes 12a and 12b near the center. The molar ratio of copper in range 87 is, for example, 1.5 to 7.5. The molar ratio of copper in range 89 is preferably more than twice the molar ratio of copper in range 85, more preferably more than three times, and even more preferably more than four times.

[0146] Additionally, before process S24, such as Figure 13 As shown in (b), the molar ratio of copper to nickel in range 81b is higher than that in range 81a. As a method to make the molar ratio of copper in range 81b greater than that in range 81a, in step S10 of forming the green sheet 30, copper is simply added to the green sheet 31 that forms the side dielectric layers 18a and 18b. In this manufacturing case, within the capacitor region 60, the molar ratio of copper to nickel in the second portion 13b, which forms the ends of the internal electrodes 12a and 12b in the Y direction, is greater than that in the first portion 13a, which forms the central portion of the internal electrodes 12a and 12b in the Y direction. Therefore, by increasing the molar ratio of copper in the internal electrodes 12a and 12b near the side edge region 66, copper diffusion itself is reduced, thus suppressing the generation of cracks caused by the aforementioned volume expansion. In particular, since the corners of the body 10 become the starting points of cracks, by suppressing the diffusion of copper to the corners, the generation of cracks can be suppressed more effectively.

[0147] In the implementation method, such as Figure 13 As shown in (a), the molar ratio of copper to nickel in the uppermost or lowermost internal electrodes 12a and 12b in the Z direction is greater than the molar ratio of copper to nickel in the central internal electrodes 12a and 12b in the Z direction. However, the molar ratio of copper to nickel can be the same in the uppermost or lowermost and central internal electrodes 12a and 12b. Figure 13 As shown in (b), the molar ratio of copper to nickel in the internal electrodes 12a and 12b within the end 65 is greater than the molar ratio of copper to nickel in the internal electrodes 12a and 12b within the central portion 61y, but the molar ratio of copper to nickel between the end 65 and the central portion 61y can also be substantially the same.

[0148] If the molar ratio of copper to nickel is the same in both the end 65 and the central portion 61y, then this step may not be necessary. Figure 6 In process S20, the side edge region 66 is formed from the laminated sheet 35.

[0149] In process S12, the metal paste does not contain copper, but it is also possible to make the metal paste contain copper.

[0150] In this embodiment, the molar ratio is measured, for example, using EDS (Energy Dispersive X-ray Spectroscopy) or WDS (Wavelength Dispersive Spectroscopy). The molar ratio of copper to nickel in the internal electrodes 12a and 12b of the end edge region 64 is set to the molar ratio of copper to nickel near the center of the end edge region 64 in the X direction. The molar ratio of copper to nickel in the internal electrodes 12a and 12b of the capacitor region 60 is set to the molar ratio of copper to nickel near the center of the capacitor region 60 in the X direction. When comparing the molar ratio of copper to nickel in the internal electrodes 12a and 12b at the portions on the end faces 51 and 52 of the end edge region 64, the molar ratio is compared at the same distance (less than 5 μm) in the X direction from the end faces 51 and 52 within the end edge region. When comparing the molar ratio of copper to nickel at the Y-direction ends 65 of the internal electrodes 12a and 12b, the molar ratio is compared at the same distance of 5 μm or less in the Y-direction from the ends of the internal electrodes 12a and 12b.

[0151] The main component is an element present in a certain component. It is sufficient to include the element present in the component to the extent that it achieves the effect of the implementation method. For example, the concentration of a certain element in a certain component is 50 mol% or more, 80 mol% or more, or 90 mol% or more.

[0152] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific embodiments described. Various modifications and alterations can be made within the scope of the spirit of the present invention.

Claims

1. A laminated ceramic electronic component, characterized in that, include: A body in which a plurality of internal electrodes, primarily composed of nickel, and a plurality of dielectric layers, primarily composed of ceramic, are alternately stacked in a first direction, the body having a pair of end faces facing each other in a second direction, the stacked plurality of internal electrodes being alternately exposed on the pair of end faces; and A pair of external electrodes, each in contact with a plurality of internal electrodes exposed from the pair of end faces, wherein the layer of the pair of external electrodes in contact with the plurality of internal electrodes is primarily composed of copper. The molar ratio of copper to nickel of the first internal electrode in the end edge region is greater than the molar ratio of copper to nickel of the first internal electrode in the capacitance region. The end edge region is the end of the body in the second direction when viewed from the first direction, and includes the first internal electrode of one of the plurality of internal electrodes exposed on one of the pair of end faces but does not include the second internal electrode exposed on the other of the pair of end faces. The capacitance region is the central part of the body in the second direction when viewed from the first direction, and the first internal electrode and the second internal electrode overlap each other in this region.

2. The laminated ceramic electronic component according to claim 1, characterized in that: Within the capacitor region, the molar ratio of copper to nickel of the outermost internal electrode in the first direction is greater than the molar ratio of copper to nickel of the internal electrode in the central part in the first direction.

3. The laminated ceramic electronic component according to claim 1 or 2, characterized in that: Within the capacitor region, the molar ratio of copper to nickel at the end of the internal electrode in a third direction that is substantially orthogonal to the first and second directions is greater than the molar ratio of copper to nickel at the center of the internal electrode in the third direction.

4. A method for manufacturing a laminated ceramic electronic component, characterized in that, include: The process of preparing a body in which multiple internal electrodes, primarily composed of nickel, and multiple dielectric layers, primarily composed of ceramic, are alternately stacked in a first direction, the body having a pair of end faces facing each other in a second direction, the stacked multiple internal electrodes being alternately exposed on the pair of end faces, the molar ratio of copper to nickel of the first internal electrode in the end edge region being greater than the molar ratio of copper to nickel of the first internal electrode in the capacitance region, the end edge region being the end of the body in the second direction when viewed from the first direction, and including the first internal electrode of one of the multiple internal electrodes exposed on the pair of end faces but excluding the second internal electrode of the other exposed on the pair of end faces, the capacitance region being the central portion of the body in the second direction when viewed from the first direction, and in this region the first internal electrode and the second internal electrode overlap each other; and The process of forming a pair of external electrodes, wherein the pair of external electrodes are in contact with the plurality of internal electrodes exposed from the pair of end faces, and the layer of the pair of external electrodes in contact with the plurality of internal electrodes is mainly composed of copper.

5. The method for manufacturing a laminated ceramic electronic component according to claim 4, characterized in that: The process of forming the pair of external electrodes includes: The process of applying metal paste in such a manner as to contact each of the plurality of internal electrodes exposed from the pair of end faces; and The process of sintering the applied metal paste.

6. The method for manufacturing a laminated ceramic electronic component according to claim 4 or 5, characterized in that: The process of preparing the main body includes: a process of preparing a laminated sheet, wherein the molar ratio of copper to the main component metal element of the ceramic in the dielectric pattern disposed in the end edge region in a manner that contacts the second internal electrode in the second direction is greater than the molar ratio of copper to the main component metal element of the ceramic in the green sheet that overlaps with the first internal electrode and the second internal electrode in the first direction; and The process of firing the laminated sheets.

7. The method for manufacturing a laminated ceramic electronic component according to any one of claims 4 to 6, characterized in that: Prior to the process of forming the external electrode, within the capacitor region, the molar ratio of copper to nickel of the outermost internal electrode in the first direction is greater than the molar ratio of copper to nickel of the internal electrode located in the center in the first direction.

8. The method for manufacturing a laminated ceramic electronic component according to any one of claims 4 to 7, characterized in that: Prior to the formation of the external electrode, within the capacitor region, the molar ratio of copper to nickel at the end of the internal electrode in a third direction substantially orthogonal to the first and second directions is greater than the molar ratio of copper to nickel at the center of the internal electrode in the third direction.

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