CERAMIC ELECTRONIC DEVICE AND MANUFACTURING METHOD OF THE SAME

A ceramic electronic device includes a multilayer chip in which each of a plurality of dielectric layers of which a main component is a ceramic and each of a plurality of internal electrode layers including Ni as a main component are alternately stacked, the multilayer chip having a rectangular parallelepiped shape, each of the plurality of internal electrode layers being exposed to two end faces opposite to each other; and external electrodes that are respectively provided on the two end faces and have a main component of Ni. The plurality of internal electrode layers include a sub metal element other than Ni, and co-materials. A concentration of the sub metal element in the plurality of internal electrode layers is higher than that in the external electrodes.

CROSS-REFERENCE TO RELATED APPLICATION

This application is based upon and claims the benefit of priority of the prior Japanese Patent Application No. 2022-042653, filed on Mar. 17, 2022 and the prior Japanese Patent Application No. 2022-042654, filed on Mar. 17, 2022, the entire contents of which are incorporated herein by reference.

FIELD

A certain aspect of the present invention relates to a ceramic electronic device and a manufacturing method of the ceramic electronic device.

BACKGROUND

Demands for miniaturization and large-capacity ceramic electronic components such as multilayer ceramic capacitors which are one of component parts continue to increase as a capacity of a battery increases in addition to multi-function and high performance of mobile terminals or other electronic devices which are represented by mobile phones.

SUMMARY OF THE INVENTION

According to an aspect of the present invention, there is provided a ceramic electronic device including: a multilayer chip in which each of a plurality of dielectric layers of which a main component is a ceramic and each of a plurality of internal electrode layers including Ni as a main component are alternately stacked, the multilayer chip having a rectangular parallelepiped shape, each of the plurality of internal electrode layers being exposed to two end faces opposite to each other; and external electrodes that are respectively provided on the two end faces and have a main component of Ni, wherein the plurality of internal electrode layers include a sub metal element other than Ni, and co-materials, and wherein a concentration of the sub metal element in the plurality of internal electrode layers is higher than that in the external electrodes.

According to another aspect of the present invention, there is provided a manufacturing method of a ceramic electronic device including: forming ceramic multilayer structure by alternately stacking each of a plurality of dielectric green sheets and each of a plurality of internal electrode patterns, the each of a plurality of dielectric green sheets including a ceramic powder, the each of a plurality of internal electrode patterns including Ni acting as a main component metal, co-materials and a sub metal element, and by making the plurality of internal electrode patterns alternately exposed to two end faces of the ceramic multilayer structure opposite to each other; applying a metal paste on the two end faces, a main component metal of the metal paste being Ni; and firing the ceramic multilayer structure so that a concentration of the sub metal element in internal electrode layers formed from the plurality of internal electrode patterns is higher than that in external electrodes formed from the metal paste.

According to an aspect of the present invention, there is provided a ceramic electronic device including: a multilayer chip in which each of a plurality of dielectric layers of which a main component is a ceramic and each of a plurality of internal electrode layers including Ni as a main component are alternately stacked, the multilayer chip having a rectangular parallelepiped shape, each of the plurality of internal electrode layers being exposed to two end faces opposite to each other; and external electrodes that are respectively provided on the two end faces, have a main component of Ni, and include a sub metal element other than Ni, and co-materials, wherein a concentration of the sub metal element in the external electrodes is higher than that in the plurality of internal electrode layers.

According to another aspect of the present invention, there is provided a manufacturing method of a ceramic electronic device including: forming ceramic multilayer structure by alternately stacking each of a plurality of dielectric green sheets including a ceramic powder and each of a plurality of internal electrode patterns including Ni acting as a main component metal, and making the plurality of internal electrode patterns alternately exposed to two end faces of the ceramic multilayer structure opposite to each other; applying a metal paste on the two end faces, a main component metal of the metal paste being Ni, the metal paste including a sub metal element other than Ni, and co-materials; and firing the ceramic multilayer structure so that a concentration of the sub metal element in external electrodes formed from the metal paste is higher than that in internal electrode layers formed from the internal electrode patterns.

DETAILED DESCRIPTION

Regarding the increase in capacity of ceramic electronic devices, measures such as material composition studies to increase the dielectric constant of the dielectric materials and thinning of dielectric layers are being taken. It is also an effective means to increase the number of layers by thinning the internal electrode layers. However, when the internal electrode layers are made thinner, the densification temperature range differs between the dielectric layers and the internal electrode layers during the firing process. In this case, the internal electrode layer may be excessively sintered, and a continuity modulus of the internal electrode layer may be degraded. Thus, the bondability between the internal electrode layers and the external electrodes may deteriorate, and desired characteristics may not be necessarily achieved.

When the external electrode and the dielectric layer are fired at the same time, the dielectric layer and the external electrode have different densification temperature ranges during the firing process. In this case, the external electrodes may be excessively sintered and contract. Thus, the bondability between the layer and the external electrode may deteriorate, and desired characteristics may not be necessarily obtained.

A description will be given of an embodiment with reference to the accompanying drawings.

(First Embodiment)FIG.1illustrates a perspective view of a multilayer ceramic capacitor100in accordance with an embodiment, in which a cross section of a part of the multilayer ceramic capacitor100is illustrated.FIG.2illustrates a cross sectional view taken along a line A-A ofFIG.1.FIG.3illustrates a cross sectional view taken along a line B-B ofFIG.1. As illustrated inFIG.1toFIG.3, the multilayer ceramic capacitor100includes a multilayer chip10having a rectangular parallelepiped shape, and a pair of external electrodes20aand20bthat are respectively provided at two end faces of the multilayer chip10facing each other. In four faces other than the two end faces of the multilayer chip10, two faces other than an upper face and a lower face of the multilayer chip10in a stacking direction are referred to as side faces. The external electrodes20aand20bextend to the upper face, the lower face and the two side faces of the multilayer chip10. However, the external electrodes20aand20bare spaced from each other.

The multilayer chip10has a structure designed to have dielectric layers11and internal electrode layers12alternately stacked. The dielectric layer11includes ceramic material acting as a dielectric material. The internal electrode layers12include a base metal material. End edges of the internal electrode layers12are alternately exposed to a first end face of the multilayer chip10and a second end face of the multilayer chip10that is different from the first end face. In the embodiment, the first end face is opposite to the second end face. The external electrode20ais provided on the first end face. The external electrode20bis provided on the second end face. Thus, the internal electrode layers12are alternately conducted to the external electrode20aand the external electrode20b. Thus, the multilayer ceramic capacitor100has a structure in which a plurality of the dielectric layers11are stacked and each two of the dielectric layers11sandwich the internal electrode layer12. In a multilayer structure of the dielectric layers11and the internal electrode layers12, two of the internal electrode layers12are positioned at outermost layers in a stacking direction. The upper face and the lower face of the multilayer structure that are the internal electrode layers12are covered by cover layers13. A main component of the cover layer13is a ceramic material. For example, a main component of the cover layer13may be the same as that of the dielectric layer11or may be different from that of the dielectric layer11.

For example, the multilayer ceramic capacitor100may have a length of 0.25 mm, a width of 0.125 mm, and a height of 0.125 mm. The multilayer ceramic capacitor100may have a length of 0.4 mm, a width of 0.2 mm, and a height of 0.2 mm. The multilayer ceramic capacitor100may have a length of 0.6 mm, a width of 0.3 mm, and a height of 0.3 mm. The multilayer ceramic capacitor100may have a length of 0.6 mm, a width of 0.3 mm, and a height of 0.110 mm. The multilayer ceramic capacitor100may have a length of 1.0 mm, a width of 0.5 mm, and a height of 0.5 mm. The multilayer ceramic capacitor100may have a length of 1.0 mm, a width of 0.5 mm, and a height of 0.1 mm. The multilayer ceramic capacitor100may have a length of 3.2 mm, a width of 1.6 mm, and a height of 1.6 mm. The multilayer ceramic capacitor100may have a length of 4.5 mm, a width of 3.2 mm, and a height of 2.5 mm. However, the size of the multilayer ceramic capacitor100is not limited to the above sizes.

A main component of the dielectric layer11is a ceramic material having a perovskite structure expressed by a general formula ABO3. The perovskite structure includes ABO3-αhaving an off-stoichiometric composition. For example, the ceramic material is such as BaTiO3(barium titanate), CaZrO3(calcium zirconate), CaTiO3(calcium titanate), SrTiO3(strontium titanate), MgTiO3(magnesium titanate), Ba1-x-yCaxSryTi1-zZrzO3(0≤x≤1, 0≤y≤1, 0≤z≤1) having a perovskite structure. Ba1-x-yCaxSryTi1-zZrzO3may be barium strontium titanate, barium calcium titanate, barium zirconate, barium titanate zirconate, calcium titanate zirconate, barium calcium titanate zirconate or the like.

The internal electrode layer12is mainly composed of Ni. The internal electrode layer12contains, in addition to Ni, which is the main component, an additive metal element at a molar ratio smaller than that of the main component. The additive metal element is not particularly limited as long as it is other than Ni. For example, the additive metal element may be one or more selected from gold (Au), tin (Sn), Cr, iron (Fe), yttrium (Y), indium (In), arsenic (As), Co, copper (Cu), iridium (Ir), Mg, osmium (Os), palladium (Pd), platinum (Pt), rhenium (Re), rhodium (Rh), ruthenium (Ru), selenium (Se), tellurium (Te), zinc (Zn), and germanium (Ge). When two or more additional metal elements are used, the total molar ratio of the additive metal elements is smaller than the molar ratio of Ni. In addition, the internal electrode layers12contain a co-material of ceramic grains. The co-material is not particularly limited, but the same material as the main component ceramic of the dielectric layer11can be used. For example, co-materials include BaTiO3(barium titanate), CaZrO3(calcium zirconate), CaTiO3(calcium titanate), SrTiO3(strontium titanate), MgTiO3(magnesium titanate), Ba1-x-yCaxSryTi1-zZrzO3(0≤x≤1, 0≤y≤1, 0≤z≤1) can be selected and used. Ba1-x-yCaxSryTi1-zZrzO3can be barium strontium titanate, barium calcium titanate, barium zirconate, barium zirconate titanate, calcium zirconate titanate and barium calcium titanate zirconate.

The external electrodes20aand20bare mainly composed of Ni. The external electrodes20aand20bmay contain the same additive metal element as the internal electrode layers12in a smaller molar ratio than the main component, in addition to Ni, which is the main component. Also, the external electrodes20aand20bmay contain a co-material of ceramic grains. Also, one or more plated layers may be formed on the surfaces of the external electrodes20aand20bopposite to the multilayer chip10.

As illustrated inFIG.2, a section, in which a set of the internal electrode layers12connected to the external electrode20aface another set of the internal electrode layers12connected to the external electrode20b, is a section generating electrical capacity in the multilayer ceramic capacitor100. Accordingly, the section is referred to as a capacity section14. That is, the capacity section14is a section in which the internal electrode layers next to each other being connected to different external electrodes face each other.

A section, in which the internal electrode layers12connected to the external electrode20aface each other without sandwiching the internal electrode layer12connected to the external electrode20b, is referred to as an end margin15. A section, in which the internal electrode layers12connected to the external electrode20bface each other without sandwiching the internal electrode layer12connected to the external electrode20ais another end margin15. That is, the end margin15is a section in which a set of the internal electrode layers12connected to one external electrode face each other without sandwiching the internal electrode layer12connected to the other external electrode. The end margins15are sections that do not generate electrical capacity in the multilayer ceramic capacitor100.

As illustrated inFIG.3, a section of the multilayer chip10from the two sides thereof to the internal electrode layers12is referred to as a side margin16. That is, the side margin16is a section covering edges of the stacked internal electrode layers12in the extension direction toward the two side faces. The side margin16does not generate electrical capacity.

The thickness of each internal electrode layer12is, for example, 0.2 μm or more and 0.8 μm or less, 0.3 μm or more and 0.8 μm or less, 0.6 μm or more and 0.8 μm or less, 0.8 μm or more and 1.5 μm or less or 1.5 μm or more and 4.0 μm or less. The thickness of the internal electrode layer12per layer is obtained by exposing, for example, the section of the multilayer ceramic capacitor100illustrated inFIG.2and calculating an average value of thicknesses of 10 different points from an image taken by using a scanning transmission electron microscope.

The thickness of the dielectric layer11per layer is, for example, 0.2 μm or more and 0.4 μm or less, or 0.4 μm or more and 0.5 μm or less, or 0.4 μm or more and 1.0 μm or less, or 1.0 μm or more and 10 μm or less. The thickness of the dielectric layer11per layer is obtained by exposing, for example, the section of the multilayer ceramic capacitor illustrated inFIG.2and calculating an average value of thicknesses of 10 different points from an image taken by using a scanning transmission electron microscope.

In order to reduce the size and increase the capacity of the multilayer ceramic capacitor100, it is conceivable to increase the capacity per unit volume by thinning the dielectric layers11and the internal electrode layers12. However, since the sintering temperature of the dielectric layers11is higher than the sintering temperature of the internal electrode layers12, when the internal electrode layers12are made thinner, the continuity modulus of the internal electrode layer12may decrease during firing in a temperature range in which the dielectric layer11is densified. In particular, the continuity modulus of the internal electrode layers12may decrease near the external electrodes20aand20b. For example, the continuity modulus of the internal electrode layers12may decrease in the end margins15. When the continuity modulus of the internal electrode layers12is lowered, the bonding between the internal electrode layers12and the external electrodes20aand20bis deteriorated, resulting in poor electrical conductivity, and there is a possibility that desired characteristics cannot be obtained.

FIG.4is a diagram illustrating the continuity modulus of the internal electrode layers12. As exemplified inFIG.4, in an observation region of length L0 in the internal electrode layer12, the lengths L1, L2, . . . , Ln are summed and ΣLn/L0 can be defined as the continuity modulus of the layer.

The multilayer ceramic capacitor100according to this embodiment has a configuration that improves the bondability between the internal electrode layers12and the external electrodes20aand20b.

First, the sintering of the internal electrode layers12is delayed because the internal electrode layers12contain the co-material. In addition to the main component Ni, the internal electrode layers12contain the additive metal element, so that the amount of the co-material remaining in the internal electrode layers12can be increased. It is considered that this is because the additive metal element segregates around the co-material grains. By using a fine and highly dispersed co-material, the amount of co-material remaining in the internal electrode layers12can be particularly increased. Since the co-material added for the purpose of delaying sintering does not diffuse into the dielectric layer11during the sintering process and remains largely in the internal electrode layers12, a sufficient sintering delay effect can be obtained and the continuity modulus of the internal electrode layer12is improved. Furthermore, in the multilayer ceramic capacitor100according to this embodiment, the concentration of the additive metal element is higher in the internal electrode layers12than in the external electrodes20aand20b. With this configuration, the additive metal element diffuses from the internal electrode layer12toward the external electrodes20aand20b, causing a flow of the additive metal element, thereby improving the bondability between the internal electrode layer12and the external electrodes20aand20b. As a result, it is possible to suppress a decrease in capacity due to poor connection and achieve desired capacity and characteristics.

Since it is preferable that there is a difference in the concentration of the additive metal element near the external electrode, it is preferable that, in each of the end margins15, the concentration of the additive metal element in the internal electrode layer12connected to the external electrode is higher than that of the external electrode.

When Au, Sn, Cr, Fe, Y, In, As, Co, Cu, Jr, Mg, Os, Pd, Pt, Re, Rh, Ru, Se, Te, Zn, and Ge are used as the additive metal elements, these additive metal elements tend to segregate around the co-material grains, and the amount of the co-material remaining in the internal electrode layers12can be increased.

If the amount of the additive metal element in the internal electrode layers12is small, there is a risk that a sufficient amount of the co-material cannot remain in the internal electrode layers12. Therefore, in the internal electrode layer12, it is preferable to set a lower limit to the additive metal element concentration. For example, in the internal electrode layer12, the additive metal element concentration is preferably 0.01 at % or more, more preferably 0.1 at % or more, and 1.0 at % or more with respect to Ni. The additive metal element concentration is the atom number ratio of the additive metal element when Ni is assumed to be 100 at %.

On the other hand, if the amount of the additive metal element in the internal electrode layer12is large, the additive metal element diffuses into the dielectric layer11, degrading the additive design of the dielectric layer11and causing the capacity and characteristic values to deviate from the design values. Therefore, in the internal electrode layer12, it is preferable to set an upper limit to the additive metal element concentration. For example, in the internal electrode layer12, the additive metal element concentration is preferably 5.0 at % or less, more preferably 3.0 at % or less, and 1.5 at % or less with respect to Ni.

From the viewpoint of setting an upper limit and a lower limit for the additive metal element concentration in the internal electrode layer12, the ratio of the additive metal element concentration in the external electrode to which the internal electrode layer is connected to the additive metal element concentration in the internal electrode layer12has an upper limit and a lower limit. For example, the ratio is preferably 0.3 or more and 0.5 or less, more preferably 0.2 or more and 0.4 or less, and 0.1 or more and 0.2 or less.

If the amount of the co-material remaining in the internal electrode layers12is small, there is a risk that the sintering retardation effect cannot be sufficiently obtained. Therefore, it is preferable to set a lower limit to the amount of the co-material in the internal electrode layers12. For example, in the internal electrode layers12, the amount of the co-material is preferably 5.0 wt % or more, more preferably 10 wt % or more, and even more preferably 15 wt % or more. The amount of the co-material is the weight ratio of the co-material when Ni is assumed to be 100 wt %.

On the other hand, if the amount of the co-material remaining in the internal electrode layers12is large, the continuity modulus of the internal electrode layers12may decrease and the electric properties may deteriorate due to diffusion of the co-material into the dielectric layers11during the sintering process. Therefore, it is preferable to set an upper limit to the amount of the co-material in the internal electrode layers12. For example, in the internal electrode layers12, the amount of the co-material is preferably 20 wt % or less, more preferably 15 wt % or less, and even more preferably 10 wt % or less.

As for the amount of the co-material remaining in the internal electrode layers12, the volume distribution of the co-material can also be used as an index. For example, as exemplified inFIG.5, the diameter of each of the plurality of co-materials remaining dispersed in the internal electrode layer12is calculated and the volume distribution is calculated so that the sum of the volumes of the co-materials calculated from the diameters are 100%. The horizontal axis indicates the diameter of each co-material. The vertical axis indicates volume distribution (%). In this distribution graph, the smaller the slope m of the straight line obtained by straight line approximation is, the more large-diameter co-materials remain. For example, the slope “m” is preferably 3.8 or more and 5.0 or less, more preferably 3.9 or more and 4.9 or less, and even more preferably 4.5 or more and 4.8 or less. The diameter of each co-material can be obtained, for example, by measuring the maximum length of each grain in an SEM (Scanning Electron Microscope) photograph of the central cross section. The volume of the grain can be calculated as the volume of the cube when the measured diameter is one side of the cube. For linear approximation, a straight line can be obtained by connecting two points of the data using the 20% value and the 80% value of the volume distribution.

Next, a description will be given of a manufacturing method of the multilayer ceramic capacitors100.FIG.6illustrates a manufacturing method of the multilayer ceramic capacitor100.

(Making process of raw material powder) A dielectric material for forming the dielectric layer11is prepared. The dielectric material includes the main component ceramic of the dielectric layer11. Generally, an A site element and a B site element are included in the dielectric layer11in a sintered phase of grains of ABO3. For example, BaTiO3is tetragonal compound having a perovskite structure and has a high dielectric constant. Generally, BaTiO3is obtained by reacting a titanium material such as titanium dioxide with a barium material such as barium carbonate and synthesizing barium titanate. Various methods can be used as a synthesizing method of the ceramic structuring the dielectric layer11. For example, a solid-phase method, a sol-gel method, a hydrothermal method or the like can be used. The embodiments may use any of these methods.

For example, the resulting ceramic raw material powder is wet-blended with additives and is dried and crushed. Thus, a ceramic material is obtained. For example, an average particle diameter of the ceramic raw material powder is preferably, 50 nm to 200 nm. For example, the particle diameter may be adjusted by crushing the resulting ceramic material as needed. Alternatively, the particle diameter of the resulting ceramic power may be adjusted by combining the crushing and classifying.

(Stacking 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 resulting dielectric material and wet-blended. With use of the resulting slurry, a dielectric green sheet52having a thickness of 0.8 μm or less is formed on a base material51by, for example, a die coater method or a doctor blade method, and then dried. The base material51is, for example, PET (polyethylene terephthalate) film.

Next, as illustrated inFIG.7A, an internal electrode pattern53is formed on the dielectric green sheet52. InFIG.7A, as an example, four parts of the internal electrode pattern53are formed on the dielectric green sheet52and are spaced from each other. The dielectric green sheet52on which the internal electrode pattern53is formed is a stack unit. The internal electrode pattern53is a paste material containing Ni powder, which is a main component metal, powder of the co-material, powder of the additive metal element, and the like.

Next, the dielectric green sheets52are peeled from the base materials51. As illustrated inFIG.8B, a predetermined number (for example, 100 to 500) of the stack units are stacked.

Next, a predetermined number (for example, 2 to 10) of a cover sheet54is stacked on an upper face and a lower face of a ceramic multilayer structure of the stacked stack units and is thermally crimped. The resulting ceramic multilayer structure is cut into a chip having a predetermined size (for example, 1.0 mm×0.5 mm). InFIG.7B, the multilayer structure is cut along a dotted line. The cover sheet54may have the same components of the dielectric green sheet52. The additive compound of the cover sheet54may be different from that of the dielectric green sheet52. A metal paste to be the external electrode is applied to both end faces of the resulting ceramic multilayer structure by a dipping or the like. The metal paste contains Ni powder, which is the main component metal, and may contain the co-material powder, the additive metal element powder, and the like. When the metal paste contains the additive metal element, the additive metal element concentration with respect to Ni is made smaller than the additive metal element concentration (concentration with respect to Ni) in the internal electrode pattern.

(Firing process) The binder is removed from the ceramic multilayer structure in N2atmosphere in a temperature range of 250 degrees C. to 500 degrees C. After that, the resulting ceramic multilayer structure is fired for 10 minutes to 2 hours in a reductive atmosphere having an oxygen partial pressure of 10−5to 10−8atm in a temperature range of 1100 degrees C. to 1300 degrees C. Thus, the multilayer ceramic capacitor100is obtained. By increasing the rate of temperature rise in the firing step, the metal material is sintered before the co-material is extruded from the metal material, so the co-material tends to remain in the internal electrode layers12. Therefore, the average rate of temperature rise from room temperature to the maximum temperature in the firing step is preferably 30° C./min or more, more preferably 45° C./min or more. If the average rate of temperature rise is too high, the organic components remaining in the ceramic multilayer structure (those that could not be removed only by the binder removal treatment) cannot be sufficiently discharged, resulting in problems such as cracks occurring during the firing process. Therefore, the average rate of temperature rise is preferably 80° C./min or less, more preferably 65° C./min or less.

(Re-oxidizing process) After that, a re-oxidation process may be performed in a N2gas atmosphere at approximately at 600 degrees C. to 1000 degrees C. so that the internal electrode layer12is not oxidized.

(Plating process) After that, by a plating process, metal coating of Cu, Ni, Sn or the like may be performed on the surface of the external electrodes20aand20b.

According to the manufacturing method according to the present embodiment, since the internal electrode pattern53contains the co-material, the sintering of the metal component contained in the internal electrode pattern53is delayed. In addition to the main component Ni, the internal electrode pattern53contains the additive metal element, so that the amount of co-material remaining in the internal electrode layer12after firing can be increased. Since the co-material added for the purpose of delaying sintering does not diffuse into the dielectric layer11during the sintering process and remains largely in the internal electrode layers12, a sufficient sintering delay effect can be obtained. Thus, the continuity modulus of the internal electrode layer12is improved. In addition, since the additive metal element concentration with respect to Ni is higher in the internal electrode pattern53than in the metal paste for forming the external electrodes, the additive metal element diffuses from the internal electrode layer12toward the external electrodes20aand20b. Since the additive metal element diffuses and flows, the bondability between the internal electrode layer12and the external electrodes20aand20bis improved. As a result, it is possible to suppress a decrease in capacity due to poor connection and achieve desired capacity and characteristics.

(Second Embodiment) A description will be given of a second embodiment. Points of the second embodiment different from the first embodiment will be described.

The external electrodes20aand20bare mainly composed of Ni. The external electrodes20aand20bcontain, in addition to Ni, which is the main component, an additive metal element at a molar ratio smaller than that of the main component. The additive metal element is not particularly limited as long as it is other than Ni. For example, the additive metal element may be one or more selected from gold (Au), tin (Sn), chromium Cr, iron (Fe), yttrium (Y), indium (In), arsenic (As), Co (cobalt), copper (Cu), iridium (Jr), Mg (magnesium), osmium (Os), palladium (Pd), platinum (Pt), rhenium (Re), rhodium (Rh), ruthenium (Ru), selenium (Se), tellurium (Te), zinc (Zn), and germanium (Ge). When two or more additional metal elements are used, the total molar ratio of the additive metal elements is smaller than the molar ratio of Ni. In addition, the external electrodes20aand20bcontain a co-material of ceramic grains. The co-material is not particularly limited, but the same material as the main component ceramic of the dielectric layer11can be used. For example, co-materials include BaTiO3(barium titanate), CaZrO3(calcium zirconate), CaTiO3(calcium titanate), SrTiO3(strontium titanate), MgTiO3(magnesium titanate), Ba1-x-yCaxSryTi1-zZrzO3(0≤x≤1, 0≤y≤1, 0≤z≤1) can be selected and used. Ba1-x-yCaxSryTi1-zZrzO3can be barium strontium titanate, barium calcium titanate, barium zirconate, barium zirconate titanate, calcium zirconate titanate and barium calcium titanate zirconate.

The internal electrode layer12is mainly composed of Ni. The internal electrode layer12may contain the same additive metal element as the external electrodes20aand20bin a smaller molar ratio than the main component, in addition to Ni, which is the main component. Also, the internal electrode layer12may contain a co-material of ceramic grains.

When the external electrodes20aand20band the dielectric layer11are fired at the same time, the dielectric layer11and the external electrodes20aand20bhave different densification temperature ranges during the firing process. Therefore, there is a risk of oversintering and shrinkage of the external electrodes20aand20b. In this case, the bondability between the internal electrode layers12and the external electrodes20aand20bis deteriorated, resulting in poor electrical conductivity and the desired characteristics may not be obtained.

Further, when the external electrodes20aand20bshrink during the firing process, the ends of the external electrodes20aand20bbecome embedded in the multilayer chip10, generating stress. As illustrated inFIG.8, cracks40may occur in the multilayer chip10.

The multilayer ceramic capacitor100according to this embodiment has a configuration that improves the bondability between the internal electrode layers12and the external electrodes20aand20b. Moreover, the multilayer ceramic capacitor100according to the present embodiment has a structure capable of suppressing the occurrence of cracks.

First, sintering of the external electrodes20aand20bis delayed because the external electrodes20aand20bcontain the co-material. In addition, the external electrodes20aand20bcontain the additive metal element in addition to Ni, which is the main component, so that the amount of co-material remaining in the external electrodes20aand20bcan be increased. It is considered that this is because the additive metal element segregates around the co-material grains. By using a fine and highly dispersed co-material, the amount of the co-material remaining in the external electrodes20aand20bcan be particularly increased. The co-material added for the purpose of delaying sintering does not diffuse into the dielectric layer11during the sintering process and remains largely in the external electrodes20aand20b. Therefore, the effect of delaying the sintering can be sufficiently achieved. Thus, the occurrence of the cracks can be suppressed. Furthermore, in the multilayer ceramic capacitor100according to this embodiment, the concentration of the additive metal element is higher in the external electrodes20aand20bthan in the internal electrode layers12. With this configuration, the additive metal element diffuses from the external electrodes20aand20btoward the internal electrode layer12, and the additive metal element flows, thereby improving the bondability between the internal electrode layer12and the external electrodes20aand20b. As a result, it is possible to suppress a decrease in capacity due to poor connection and achieve desired capacity and characteristics. By diffusing the additive metal element into the internal electrode layer12containing the co-material, a sintering delay effect can be obtained also in the internal electrode layer12, so that the bondability between the internal electrode layer12and the external electrodes20aand20bis improved.

Since it is preferable that there is a difference in the concentration of the additive metal element near the external electrode, the concentration of the additive metal element in each of the end margins15is higher than that of the internal electrode layer12, which is connected to the internal electrode layer.

When Au, Sn, Cr, Fe, Y, In, As, Co, Cu, Ir, Mg, Os, Pd, Pt, Re, Rh, Ru, Se, Te, Zn, and Ge are used as additive metal elements, these additive metal elements tend to segregate around the material grains, and the amount of co-material remaining in the external electrodes20aand20bcan be increased.

If the amount of the additive metal element in the external electrodes20aand20bis small, there is a possibility that a sufficient amount of the co-material cannot remain in the external electrodes20aand20b. Therefore, in the external electrodes20aand20b, it is preferable to set a lower limit to the additive metal element concentration. For example, in the external electrodes20aand20b, the additive metal element concentration is preferably 0.01 at % or more, more preferably 0.1 at % or more, and 1.0 at % or more with respect to Ni. The additive metal element concentration is the atom number ratio of the additive metal element when Ni is assumed to be 100 at %.

On the other hand, if the amount of the additive metal element in the external electrodes20aand20bis large, the additive metal element diffuses into the dielectric layer11, degrading the additive design of the dielectric layer11and causing the capacity and characteristic values to deviate from the design values. Therefore, it is preferable to set an upper limit to the additive metal element concentration in the external electrodes20aand20b. For example, in the external electrodes20aand20b, the additive metal element concentration is preferably 5.0 at % or less, more preferably 3.0 at % or less, and 1.5 at % or less with respect to Ni.

From the viewpoint of setting upper and lower limits for the additive metal element concentration in the external electrodes20aand20b, it is preferable that the ratio of the additive metal element concentration in the internal electrode layer12to which the external electrodes are connected to the additive metal element concentration in the external electrodes20aand20bhas an upper limit and a lower limit. For example, the ratio is preferably 0.3 or more and 0.5 or less, more preferably 0.2 or more and 0.4 or less, and 0.1 or more and 0.2 or less.

If the amount of the co-material remaining in the external electrodes20aand20bis small, there is a risk that a sufficient sintering delay effect cannot be obtained. Therefore, in the external electrodes20aand20b, it is preferable to set a lower limit to the amount of the co-material. For example, in the external electrodes20aand20b, the amount of the co-material is preferably 10 wt % or more, more preferably 15 wt % or more, and even more preferably 25 wt % or more. The amount of the co-material is the weight ratio of the co-material when Ni is assumed to be 100 wt %.

On the other hand, if the amount of the co-material remaining in the external electrodes20aand20bis large, the number of locations where the contraction is delayed locally increases, and contraction stress accumulates from these locations, which may induce cracks from inside the external electrode. Therefore, it is preferable to set an upper limit on the amount of the co-material in the external electrodes20aand20b. For example, in the external electrodes20aand20b, the amount of the co-material is preferably 40 wt % or less, more preferably 35 wt % or less, and even more preferably 30 wt % or less.

As for the amount of the co-material remaining in the external electrodes20aand20b, the volume distribution of the co-material can also be used as an index. For example, as exemplified inFIG.9, the diameter of each of the plurality of co-materials remaining dispersed in the internal electrode layer12is calculated and the volume distribution is calculated so that the sum of the volumes of the co-materials calculated from the diameters are 100%. The horizontal axis indicates the diameter of each co-material. The vertical axis indicates volume distribution (%). In this distribution graph, the smaller the slope “m” of the straight line obtained by straight line approximation is, the more large-diameter co-materials remain. For example, the slope “m” is preferably 3.8 or more and 5.0 or less, more preferably 3.9 or more and 4.9 or less, and even more preferably 4.5 or more and 4.8 or less. The diameter of each co-material can be obtained, for example, by measuring the maximum length of each grain in an SEM (Scanning Electron Microscope) photograph of the central cross section. The volume of the grain can be calculated as the volume of the cube when the measured diameter is one side of the cube. For linear approximation, a straight line can be obtained by connecting two points of the data using the 20% value and the 80% value of the volume distribution.

Next, a description will be given of a manufacturing method of the multilayer ceramic capacitors100.FIG.10illustrates a manufacturing method of the multilayer ceramic capacitor100.

(Making process of raw material powder) A dielectric material for forming the dielectric layer11is prepared. The dielectric material includes the main component ceramic of the dielectric layer11. Generally, an A site element and a B site element are included in the dielectric layer11in a sintered phase of grains of ABO3. For example, BaTiO3is tetragonal compound having a perovskite structure and has a high dielectric constant. Generally, BaTiO3is obtained by reacting a titanium material such as titanium dioxide with a barium material such as barium carbonate and synthesizing barium titanate. Various methods can be used as a synthesizing method of the ceramic structuring the dielectric layer11. For example, a solid-phase method, a sol-gel method, a hydrothermal method or the like can be used. The embodiments may use any of these methods.

An additive compound may be added to the resulting ceramic powder, in accordance with purposes. The additive compound may be an oxide of molybdenum (Mo), niobium (Nb), tantalum (Ta), tungsten (W), magnesium (Mg), manganese (Mn), 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 an oxide of cobalt (Co), nickel (Ni), lithium (Li), boron (B), sodium (Na), potassium (K) or silicon (Si), or a glass including cobalt, nickel, lithium, boron, sodium, potassium or silicon. SiO2mainly acts as a sintering assistant.

For example, the resulting ceramic raw material powder is wet-blended with additives and is dried and crushed. Thus, a ceramic material is obtained. For example, an average particle diameter of the ceramic raw material powder is preferably, 50 nm to 200 nm. For example, the particle diameter may be adjusted by crushing the resulting ceramic material as needed. Alternatively, the particle diameter of the resulting ceramic power may be adjusted by combining the crushing and classifying.

(Stacking 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 resulting dielectric material and wet-blended. With use of the resulting slurry, the dielectric green sheet52having a thickness of 0.8 μm or less is formed on the base material51by, for example, a die coater method or a doctor blade method, and then dried. The base material51is, for example, PET (polyethylene terephthalate) film.

Next, as illustrated inFIG.11A, the internal electrode pattern53is formed on the dielectric green sheet52. InFIG.11A, as an example, four parts of the internal electrode pattern53are formed on the dielectric green sheet52and are spaced from each other. The dielectric green sheet52on which the internal electrode pattern53is formed is a stack unit. The internal electrode pattern53is a paste material containing Ni powder, which is a main component metal, powder of the co-material, powder of the additive metal element, and the like. When the additive metal element is added to the internal electrode pattern53, the concentration of the additive metal element with respect to Ni is made smaller than the concentration of the additive metal element (with respect to Ni) in the metal paste for forming the external electrodes.

Next, the dielectric green sheets52are peeled from the base materials51. As illustrated inFIG.11B, a predetermined number (for example, 100 to 500) of the stack units are stacked.

Next, a predetermined number (for example, 2 to 10) of the cover sheet54is stacked on an upper face and a lower face of a ceramic multilayer structure of the stacked stack units and is thermally crimped. The resulting ceramic multilayer structure is cut into a chip having a predetermined size (for example, 1.0 mm×0.5 mm). InFIG.11B, the multilayer structure is cut along a dotted line. The cover sheet54may have the same components of the dielectric green sheet52. The additive compound of the cover sheet54may be different from that of the dielectric green sheet52. A metal paste to be the external electrode is applied to both end faces of the resulting ceramic multilayer structure by a dipping or the like. The metal paste contains Ni powder, which is the main component metal, and may contain the co-material powder, the additive metal element powder, and the like.

(Firing process) The binder is removed from the ceramic multilayer structure in N2atmosphere in a temperature range of 250 degrees C. to 500 degrees C. After that, the resulting ceramic multilayer structure is fired for 10 minutes to 2 hours in a reductive atmosphere having an oxygen partial pressure of 10−5to 10−8atm in a temperature range of 1100 degrees C. to 1300 degrees C. Thus, the multilayer ceramic capacitor100is obtained. By increasing the rate of temperature rise in the firing step, the metal material is sintered before the co-material is extruded from the metal material, so the co-material tends to remain in the external electrodes20aand20b. Therefore, the average rate of temperature rise from room temperature to the maximum temperature in the firing step is preferably 30° C./min or more, more preferably 45° C./min or more. If the average rate of temperature rise is too high, the organic components remaining in the ceramic multilayer structure (those that could not be removed only by the binder removal treatment) cannot be sufficiently discharged, resulting in problems such as cracks occurring during the firing process. Therefore, the average rate of temperature rise is preferably 80° C./min or less, more preferably 65° C./min or less.

(Re-oxidizing process) After that, a re-oxidation process may be performed in a N2gas atmosphere at approximately at 600 degrees C. to 1000 degrees C. so that the internal electrode layer12is not oxidized.

(Plating process) After that, by a plating process, metal coating of Cu, Ni, Sn or the like may be performed on the surface of the external electrodes20aand20b.

According to the manufacturing method according to the present embodiment, since the metal paste for forming the external electrodes contains the co-material, the sintering of the metal component contained in the metal paste is delayed. In addition to the main component Ni, the metal paste contains the additive metal element, so that the amount of co-material remaining in the external electrodes20aand20bafter firing can be increased. Since the co-material added for the purpose of delaying sintering does not diffuse into the dielectric layer11during the sintering process and remains largely in the external electrodes, a sufficient sintering delay effect can be obtained. Thus, the occurrence of the cracks is suppressed. In addition, since the additive metal element concentration with respect to Ni is higher in the metal paste than in the internal electrode pattern53, the additive metal element diffuses from the external electrodes20aand20btoward the internal electrode layer12. Since the additive metal element diffuses and flows, the bondability between the internal electrode layer12and the external electrodes20aand20bis improved. When the co-material contained in the external electrodes20aand20band the dielectric layer11and the cover layer13are the same material, the dielectric layer11and the cover layer13are integrated at the boundaries between the multilayer chip10and the external electrodes20aand20bthrough a sintering process. Therefore, the adhesion of the external electrodes20aand20bis improved. As a result, it is possible to prevent a decrease in capacity due to poor connection and the formation of pores and the like at the boundary, so that it is possible to obtain effects such as less penetration of moisture into the boundary, and the desired capacity and characteristics can be achieved. By diffusing the additive metal element into the internal electrode layer12containing the co-material, a sintering delay effect can be obtained also in the internal electrode layer12, so that the bondability between the internal electrode layer12and the external electrodes20aand20bis improved.

In the embodiments, the multilayer ceramic capacitor is described as an example of ceramic electronic devices. However, the embodiments are not limited to the multilayer ceramic capacitor. For example, the embodiments may be applied to another electronic device such as varistor or thermistor.

EXAMPLES

Hereinafter, the multilayer ceramic capacitor according to the embodiment was manufactured and its characteristics were investigated.

(Example 1) A stack unit was obtained by forming a dielectric green sheet containing barium titanate as a dielectric material and printing an internal electrode pattern containing Ni powder, a co-material, and an additive metal element. 200 numbers of the stack units were stacked, crimped and cut. After removing the binder, a metal paste for external electrodes containing Ni powder and a co-material was applied to the two end faces of the stack units, and fired in a reducing atmosphere. BaTiO3was used as the co-material for the internal electrode pattern and the metal paste. Au was used as the additive metal element for the internal electrode pattern. The amount of Au added to the internal electrode pattern was set to 1.0 at % when Ni was assumed to be 100 at %.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in external electrode before forming plated layer)/(concentration of additive metal element in internal electrode layer) at the end margin was 0.52. The end margin is a part of the end margin15illustrated inFIG.2. The additive metal element was detected by EDS (energy dispersive X-ray spectroscopy), and (amount of additive metal element detected in external electrode)/(detected amount of additive metal element in internal electrode layer) was used as the ratio. The EDS analysis in this case is a point analysis, and the detected amount is the detected amount at a predetermined irradiation point. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 4.64.

(Example 2) In Example 2, Sn was used as the additive metal element. The amount of Sn added to the internal electrode pattern was set to 1.0 at % when Ni was assumed to be 100 at %. Other conditions were the same as in Example 1.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in external electrode before forming plated layer)/(concentration of additive metal element in internal electrode layer) at the end margin was 0.28. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 3.90.

(Example 3) In Example 3, Cr was used as the additive metal element. The amount of Cr added to the internal electrode pattern was set to 1.0 at % when Ni was assumed to be 100 at %. Other conditions were the same as in Example 1.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in external electrode before forming plated layer)/(concentration of additive metal element in internal electrode layer) at the end margin was 0.51. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 4.56.

(Example 4) In Example 4, Fe was used as the additive metal element. The amount of Fe added to the internal electrode pattern was set to 1.0 at % when Ni was assumed to be 100 at %. Other conditions were the same as in Example 1.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in external electrode before forming plated layer)/(concentration of additive metal element in internal electrode layer) at the end margin was 0.43. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 3.80.

(Example 5) In Example 5, Y was used as the additive metal element. The amount of Y added to the internal electrode pattern was set to 1.0 at % when Ni was assumed to be 100 at %. Other conditions were the same as in Example 1.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in external electrode before forming plated layer)/(concentration of added metal element in internal electrode layer) at the end margin was 0.44. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 3.95.

(Example 6) In Example 6, In was used as the additive metal element. The amount of In added to the internal electrode pattern was set to 1.0 at % when Ni was assumed to be 100 at %. Other conditions were the same as in Example 1.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in external electrode before forming plated layer)/(concentration of additive metal element in internal electrode layer) at the end margin was 0.43. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 3.85.

(Example 7) In Example 7, Au and Sn were used as the additive metal elements. The amounts of Au and Sn added to the internal electrode pattern were set to 0.5 at % and 1.0 at %, respectively, assuming 100 at % of Ni. Other conditions were the same as in Example 1.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in external electrode before forming plated layer)/(concentration of additive metal element in internal electrode layer) at the end margin was 0.53. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 4.77.

(Example 8) In Example 8, Au and Cr were used as the additive metal elements. The amounts of Au and Cr added to the internal electrode pattern were set to 0.5 at % and 1.0 at %, respectively, assuming 100 at % of Ni. Other conditions were the same as in Example 1.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in external electrode before forming plated layer)/(concentration of additive metal element in internal electrode layer) at the end margin was 0.52. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 4.66.

(Example 9) In Example 9, Au, Sn, and Cr were used as additive metal elements. The amounts of Au, Sn, and Cr added to the internal electrode pattern were set to 0.5 at %, 0.5 at %, and 1.0 at %, respectively, assuming 100 at % of Ni. Other conditions were the same as in Example 1.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in external electrode before forming plated layer)/(concentration of additive metal element in internal electrode layer) at the end margin was 0.54. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 4.79.

(Comparative Example 1) In Comparative Example 1, no additive metal element was added to the internal electrode pattern. Other conditions were the same as in Example 1.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 6.39.

FIG.12Ais a diagram obtained by tracing the SEM photograph of the cross section in the stacking direction of Example 1. FIG.FIG.12Bis a diagram obtained by tracing the SEM photograph of a cross section in the stacking direction of Comparative Example 1. In comparison withFIG.12B, it can be seen that a large amount of co-material17remains in the internal electrode layer12inFIG.12A.

FIG.13is a graph calculated from the diameter and volume distribution of the co-material in the internal electrode layer for Example 1 and Comparative Example 1. As shown inFIG.13, it can be seen that the slope “m” is smaller in Example 1 than in Comparative Example 1. Therefore, it can be seen that a larger amount of the co-material remains in Example 1 than in Comparative Example 1. It is considered that this is because the additive metal element was added to the internal electrode pattern. In addition, 500 co-materials were counted in Comparative Example 1, and 500 co-materials were counted in Example 1.

(Continuity modulus) The continuity modulus of the internal electrode layers was measured for Examples 1 to 9 and Comparative Example 1. Continuity modulus was determined by embedding a fired multilayer ceramic capacitor in resin and polishing the multilayer ceramic capacitor to the central portion, thereby exposing the cross section. The cross section was observed with an SEM, about 10 images were taken, and the continuity modulus was measured from the taken images. The continuity modulus of Examples 1 to 9 was higher than that of Comparative Example 1. It is considered that this is because a large amount of the co-material remained in the internal electrode layers, and the contraction of the internal electrode layers was sufficiently delayed.

(Bondability) The bondability between the internal electrode layers and the external electrodes was examined for Examples 1 to 9 and Comparative Example 1. The state of connection between the internal electrode layers and the external electrodes was confirmed from a polished cross-sectional image in comparison with a multilayer ceramic capacitor in which no additive element was added to Ni. For example, in the case of a 200-layer stacked multilayer ceramic capacitor, if it was possible to confirm that the bonding state was improved by 15% or more compared to the multilayer ceramic capacitor in which no additive metal element was added to Ni, the bondability was judged to be very good “double circle”. If the improvement of the bonding state by 10% or more was confirmed, the bondability was judged to be good “∘”. If it was less than 10% or the same level as the multilayer ceramic capacitor in which no additive metal element was added to Ni, the bondability was judged to be bad “-”. The bondability of Comparative Example 1 was judged to be bad. It is considered that this was because no additive metal element was added. Note that the bonding state expressed here indicates a state in which the internal electrode and the external electrode are connected on the polished cross-sectional image. In contrast, in Examples 1 to 9, the bondability was judged to be very good or good. It is considered that this was because the additive metal element was diffused by making the additive metal element concentration in the internal electrode layer higher than the additive metal element concentration in the external electrode layer.

(Capacity) The capacity was measured for each of Examples 1 to 9 and Comparative Example 1. The capacity was measured using an LCR meter under conditions of 0.5 V and 1 kHz, and the average value of 100 samples was calculated. If the average capacity value was improved by 10% or more compared to the multilayer ceramic capacitor in which no additive metal element was added to Ni, the capacity was judged to be very good “double circle”. If the average capacity value was improved by 5% or more and less than 10%, the capacity was judged to be good “∘”. If the average capacity value was improved by less than 5%, the capacity was judged to be bad “-”. In Comparative Example 1, the capacity was determined to be bad. In contrast, in Examples 1 to 9, the capacity was judged to be very good or good. It is considered that this was because the continuity modulus of the internal electrode layers was higher than that of Comparative Example 1, and the bondability between the internal electrode layers and the external electrodes was also good.

(Reliability) The reliability was examined for each of Examples 1 to 9 and Comparative Example 1. Reliability was determined by performing a HALT test at 6V-125° C. For the HALT life, an average value of 100 samples was calculated. If the average value of life is more than twice that of the multilayer ceramic capacitor in which no additive metal element was added to N, the reliability was judged to be very good “double circle”. If the average value of life was 1.5 times or more, the reliability was judged to be good “∘”. If the average value of life was equal to or less than 1.5 times, the reliability was judged to be bad “-”. The reliability of Comparative Example 1 was judged to be bad. In contrast, the reliability of Examples 1 to 9 was judged to be very good or good. It is considered that this was because the bondability between the internal electrode layers and the external electrodes was also better than in Comparative Example 1. Table 1 and Table 2 show the results.

(Example 10) A stack unit was obtained by forming a dielectric green sheet containing barium titanate as a dielectric material and printing an internal electrode pattern containing Ni powder and a co-material. 200 numbers of stack units were stacked, crimped and cut. After the binder was removed, a metal paste for external electrodes containing Ni powder, a co-material, and an additive metal element was applied to the two end faces of the stack units and fired in a reducing atmosphere. BaTiO3was used as a co-material for the internal electrode pattern and the metal paste. Au was used as the additive metal element of the metal paste for the external electrodes. The amount of Au added to the metal paste was set to 1.0 at % when Ni was assumed to be 100 at %.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in internal electrode layer)/(concentration of additive metal element in external electrode before forming plating layer) at the end margin was 0.52. The end margin is a part of the end margin15illustrated inFIG.2. The additive metal element was detected by EDS (energy dispersive X-ray spectroscopy), and (amount of additive metal element detected in internal electrode layer)/(detected amount of additive metal element in external electrode) was used as the ratio. The EDS analysis in this case was a point analysis, and the detected amount was the detected amount at a predetermined irradiation point. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 4.64.

(Example 11) In Example 11, Sn was used as the additive metal element. The amount of Sn added to the metal paste for external electrodes was set to 1.0 at % when Ni was assumed to be 100 at %. Other conditions were the same as in Example 10.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in internal electrode layer)/(concentration of additive metal element in external electrode before forming plated layer) at the end margin was 0.28. The slope” “m of the graph calculated from the diameter and volume distribution of the co-material was 3.90.

(Example 12) In Example 12, Cr was used as the additive metal element. The amount of Cr added to the metal paste for external electrodes was set to 1.0 at % when Ni was assumed to be 100 at %. Other conditions were the same as in Example 10.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in internal electrode layer)/(concentration of additive metal element in external electrode before forming plated layer) at the end margin was 0.51. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 4.56.

(Example 13) In Example 13, Fe was used as the additive metal element. The amount of Fe added to the metal paste for external electrodes was set to 1.0 at % when Ni was assumed to be 100 at %. Other conditions were the same as in Example 10.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in internal electrode layer)/(concentration of additive metal element in external electrode before forming plating layer) at the end margin was 0.43. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 3.80.

(Example 14) In Example 14, Y was used as the additive metal element. The amount of Y added to the metal paste for the external electrodes was set to 1.0 at % when Ni was assumed to be 100 at %. Other conditions were the same as in Example 10.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After sintering, (concentration of additive metal element in internal electrode layer)/(concentration of additive metal element in external electrode before forming plated layer) at the end margin was 0.44. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 3.95.

(Example 15) In Example 15, In was used as the additive metal element. The amount of In added to the metal paste for external electrodes was set to 1.0 at % when Ni was assumed to be 100 at %. Other conditions were the same as in Example 10.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in internal electrode layer)/(concentration of additive metal element in external electrode before forming plated layer) at the end margin was 0.43. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 3.85.

(Example 16) In Example 16, Au and Sn were used as the additive metal elements. The amounts of Au and Sn added to the metal paste for external electrodes were set to 0.5 at % and 1.0 at %, respectively, assuming 100 at % of Ni. Other conditions were the same as in Example 10.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After sintering, (concentration of additive metal element in internal electrode layer)/(concentration of additive metal element in external electrode before forming plated layer) at the end margin was 0.53. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 4.77.

(Example 17) In Example 17, Au and Cr were used as the additive metal elements. The amounts of Au and Cr added to the metal paste for external electrodes were set to 0.5 at % and 1.0 at %, respectively, assuming 100 at % of Ni. Other conditions were the same as in Example 10.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in internal electrode layer)/(concentration of additive metal element in external electrode before forming plated layer) at the end margin was 0.52. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 4.66.

(Example 18) In Example 18, Au, Sn, and Cr were used as additive metal elements. The amounts of Au, Sn, and Cr added to the metal paste for external electrodes were set to 0.5 at %, 0.5 at %, and 1.0 at %, respectively, assuming 100 at % of Ni. Other conditions were the same as in Example 10.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. After firing, (concentration of additive metal element in internal electrode layer)/(concentration of additive metal element in external electrode before forming plated layer) at the end margin was 0.54. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 4.79.

(Comparative Example 2) In Comparative Example 2, no additive metal element was added to the metal paste for the external electrodes. Other conditions were the same as in Example 10.

The thickness of the dielectric layer after firing was 0.6 μm, and the thickness of the internal electrode layer was 0.7 μm. The slope “m” of the graph calculated from the diameter and volume distribution of the co-material was 6.39.

FIG.14Ais a diagram obtained by tracing a cross-sectional SEM photograph of the external electrode of Example 10. FIG.FIG.14Bis a diagram obtained by tracing a cross-sectional SEM photograph of the external electrode of Comparative Example 2. In comparison withFIG.14B, it can be seen that much of the co-material17remains in the external electrodes inFIG.14A.

FIG.15is a graph calculated from the diameter and volume distribution of the co-material in the external electrodes for Example 10 and Comparative Example 2. As shown inFIG.15, it can be seen that the slope “m” is smaller in Example 10 than in Comparative Example 2. Therefore, it can be seen that a larger amount of co-material remains in Example 10 than in Comparative Example 2. It is considered that this was because the additive metal element was added to the metal paste for the external electrodes. In Comparative Example 2, 500 co-materials were counted. And in Example 10, 500 co-materials were counted.

(Bondability) For Examples 10 to 18 and Comparative Example 2, the bondability between the internal electrode layer and the external electrode was examined. The state of connection between the internal electrode layers and the external electrodes was confirmed from polished cross-sectional images in comparison with a multilayer ceramic capacitor in which no additive metal element was added to Ni. For example, in the case of a 200-layer multilayer ceramic capacitor, if it was possible to confirm that the bonding state was improved by 15% or more compared to the multilayer ceramic capacitor in which no additive metal element was added to N, the bondability was judged to be very good “double circle”. If the improvement of the bonding state by 10% or more can be confirmed, the bondability was judged to be good “∘”. If the improvement was less than 10% or the same level as the multilayer ceramic capacitor in which no additive metal element was added to Ni, the bondability was judged to be bad “-”. In Comparative Example 2, the bondability was judged to be bad. It is thought that this was because the additive metal element diffused more than in Comparative Example 2 because the additive metal element concentration in the external electrode was higher than the additive metal element concentration in the internal electrode layer. Note that the bonding state expressed here indicates a state in which the internal electrode and the external electrode are connected on the polished cross-sectional image.

(Presence or absence of cracks) For each of Examples 10 to 18 and Comparative Example 2, 3000 samples were examined for cracks. A stereoscopic microscope was used to confirm the position of crack generation. If the sample occurrence rate was 0% (if no cracks were found), it was determined that cracks were not present, and if even one crack was found, cracks were determined to be present. In Comparative Example 2, cracks were determined to be “presence”. It is believed that this was because in Comparative Example 2, no additive metal element was added to the metal paste for the external electrodes, so that the sintering delay effect was not obtained. On the other hand, in Examples 10 to 18, crack generation was judged to be “absence”. It is thought that this was because in Examples 10 to 18, the sintering delay effect was sufficiently obtained by adding the additive metal element to the metal paste for the external electrodes.

(Capacity) The capacity was measured for each of Examples 10 to 18 and Comparative Example 2. The capacity was measured using an LCR meter under conditions of 0.5 V and 1 kHz, and the average value of 100 samples was calculated. If the average capacity value was improved by 10% or more compared to the multilayer ceramic capacitor in which no additive metal element was added to N, the capacity was judged to be very good “double circle”. If the average capacity value was improved by 5% or more and less than 10%, the capacity was judged to be good “∘”. If the average capacity value was improved by less than 5%, the capacity was judged to be bad “-”. In Comparative Example 2, the capacity was judged to be bad. In contrast, in Examples 10 to 18, the capacity was judged to very good or good. It is considered that this was because the continuity modulus of the internal electrode layers was higher than in Comparative Example 2, and the bondability between the internal electrode layers and the external electrodes was also good.

(Reliability) The reliability of each of Examples 10 to 18 and Comparative Example 2 was examined. Reliability was determined by performing a HALT test at 6V-125° C. For the HALT life, an average value of 100 samples was calculated. If the average value of life was more than twice that of the multilayer ceramic capacitor in which no additive metal element was added to Ni, the reliability was judged to be very good “double circle”. If the average value of life was 1.5 times or more, the reliability was judged to be good “∘”. If the average value of life was the same or improved by less than 1.5 times, the reliability was judged to be bad “-”. In Comparative Example 2, the reliability was judged to be bad. In contrast, in Examples 10 to 18, the reliability was judged to be very good or good. It is thought that this was because the bondability between the internal electrode layers and the external electrodes was better than in Comparative Example 2. Table 3 and Table 4 show the results.