Multilayer Ceramic Capacitors

Abstract

The present invention provides a multilayered ceramic capacitor in which a dielectric layer is made even thinner, and which exhibits excellent reliability even when a voltage of high field intensity is applied thereto.　Provided is a multilayered ceramic capacitor (1) comprising a plurality of first inner electrodes (4) and a plurality of second inner electrodes (5) which are disposed alternatingly along the stacking direction of a laminate (2), wherein polarity which is based on the direction of application of voltage between a first external electrode (6) and a second external electrode (7) is set such that the first inner electrodes (4) are positive electrodes and the second inner electrodes (5) are negative electrodes. The first inner electrodes (4) have a first metallic composition including Ni and Sn, and the second inner electrodes (5) have a second metallic composition including Ni. The second metallic composition may contain only Ni, or may contain Ni as a main component and contain, as an added component, at least one metal element which is selected from among Au, Pt, Ir, Pd, Os, Ag, Rh, Ru, and Cu and which has a higher normal electrode potential than Ni.

Description

[Technical field]

[0001] The present invention relates to a multilayer ceramic capacitor, and more particularly to the metal composition of internal electrodes provided in the multilayer ceramic capacitor. [Background technology]

[0002] With the recent advances in electronics technology, multilayer ceramic capacitors are required to be smaller and have higher capacitance. To meet these demands, progress is being made in thinning the dielectric layers of multilayer ceramic capacitors. However, when the dielectric layers are made thinner, the electric field strength applied to each layer becomes relatively higher. Therefore, there is a demand for improved reliability when voltage is applied.

[0003] A multilayer ceramic capacitor generally comprises a laminate having a plurality of laminated dielectric layers and a plurality of internal electrodes arranged along the interfaces between the dielectric layers, and a plurality of external electrodes provided on the outer surface of the laminate and electrically connected to the internal electrodes. Here, it is known that the internal electrodes are mainly composed of Ni, as described in, for example, JP-A-11-283867 (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 11-283867 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when the main component of the internal electrodes is Ni, there is a problem in that the reliability when a voltage is applied is still insufficient to meet the recent demands for miniaturization and large capacity.

[0006] The present invention has been made in view of the above problems, and has an object to provide a multilayer ceramic capacitor in which the dielectric layers are made even thinner and which exhibits excellent reliability even when a voltage of high electric field strength is applied. [Means for solving the problem]

[0007] The multilayer ceramic capacitor of the present invention comprises a laminate having a plurality of laminated dielectric layers made of ceramic and a plurality of internal electrodes respectively arranged along a plurality of interfaces between the dielectric layers, and a plurality of external electrodes provided on the outer surface of the laminate and electrically connected to the internal electrodes.

[0008] The internal electrodes include a plurality of first internal electrodes and a plurality of second internal electrodes arranged alternately in the stacking direction of the laminate, and the external electrodes include a first external electrode electrically connected to the first internal electrodes and a second external electrode electrically connected to the second internal electrodes.

[0009] In order to solve the above-mentioned technical problem, in this invention, the polarity is determined based on the application direction of the voltage applied between the first external electrode and the second external electrode, so that the first internal electrode is a positive electrode and the second internal electrode is a negative electrode, and the first internal electrode has a first metal composition containing Ni and Sn, and the second internal electrode has a second metal composition containing Ni. The second metal composition of the second internal electrode is mainly composed of Ni, and contains at least one metal element selected from Au, Pt, Ir, Pd, Os, Ag, Rh, Ru, and Cu, which has a higher standard electrode potential than Ni, as an additive component. It is characterized by:

[0010] The first metal composition and the second metal composition are different from each other, differing in at least one of the types and contents of the constituent elements. Effect of the Invention

[0011] According to the present invention, it is possible to suppress deterioration of the insulation of a multilayer ceramic capacitor when a voltage is applied thereto, and therefore it is possible to obtain a multilayer ceramic capacitor with excellent reliability.

[0012] Furthermore, since the first metal composition of the first internal electrodes contains Sn, the reliability of the multilayer ceramic capacitor when a voltage is applied thereto can be further improved.

[0013] In addition, since the first and second internal electrodes contain Ni, the melting point can be made higher than when the main component is, for example, Cu. This allows the first and second internal electrodes to be made thinner, so that the number of layers can be increased while maintaining the external dimensions of the multilayer ceramic capacitor, resulting in a higher obtained capacitance. [Brief description of the drawings]

[0014] [Figure 1] 1 is a cross-sectional view that typically illustrates a multilayer ceramic capacitor 1 according to an embodiment of the present invention. [Diagram 2] 2 is a diagram for explaining the standard electrode potential of the metal elements contained in each of the first internal electrode (positive electrode) 4 and the second internal electrode (negative electrode) 5 in the multilayer ceramic capacitor 1 shown in FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Hereinafter, with reference to FIG. 1, a structure of a multilayer ceramic capacitor 1 according to one embodiment of the present invention will be described.

[0016] The multilayer ceramic capacitor 1 includes a laminate 2. The laminate 2 includes a plurality of laminated dielectric layers 3 made of ceramic, and a plurality of internal electrodes 4 and 5 arranged along the interfaces between the plurality of dielectric layers 3. The internal electrodes 4 and 5 are classified into a plurality of first internal electrodes 4 and a plurality of second internal electrodes 5 arranged alternately in the lamination direction of the laminate 3. External electrodes 6 and 7 are provided on the outer surface of the laminate 2, more specifically, on each of the opposing end faces. The external electrodes 6 and 7 are classified into a first external electrode 6 electrically connected to the first internal electrode 4, and a second external electrode 7 electrically connected to the second internal electrode 5.

[0017] The composition of the internal electrodes 4 and 5 will be described later. The external electrodes 6 and 7 have Ag or Cu as the main conductive component. The dielectric layer 3 is preferably made of a dielectric ceramic containing a perovskite compound containing Ba and Ti as the main component (wherein Ba may be partially substituted with Ca and Ti may be partially substituted with Zr). In particular, when the main component of the dielectric layer 3 is BaTiO3, a high dielectric constant is exhibited and the multilayer ceramic capacitor 1 exhibits excellent reliability. In addition to the above main components, the dielectric layer 3 may contain, for example, rare earth elements, Mn, Mg, Si, etc. as secondary components.

[0018] The raw powder of the dielectric ceramic is prepared, for example, by a solid-phase synthesis method. Specifically, first, compound powders such as oxides and carbonates containing the constituent elements of the main components are mixed in a predetermined ratio and calcined. In addition to the solid-phase synthesis method, a hydrothermal method or the like may be applied. In addition, the dielectric ceramic may contain alkali metals, transition metals, Cl, S, P, Hf, etc., within the range of amounts that do not impair the effects of the present invention.

[0019] The multilayer ceramic capacitor 1 is produced, for example, as follows. A ceramic slurry is produced using the dielectric ceramic raw material powder obtained as described above. Next, ceramic green sheets are formed by a sheet forming method or the like. Next, a conductive paste to become each of the internal electrodes 4 and 5 is applied by printing or the like onto a predetermined one of the plurality of ceramic green sheets. Next, the plurality of ceramic green sheets are stacked and then pressed together to obtain a green laminate. Next, the green laminate is fired. In this firing step, a dielectric layer 3 made of a dielectric ceramic is obtained. After that, the external electrodes 6 and 7 are formed on the end faces of the laminate 3 by baking or the like.

[0020] The first feature of the multilayer ceramic capacitor 1 is that the polarity is determined based on the direction of application of a voltage between the first external electrode 6 and the second external electrode 7 so that the first internal electrode 4 is a positive electrode and the second internal electrode 5 is a negative electrode during actual use. Therefore, although not shown, it is preferable that a mark indicating the polarity is provided on, for example, the outer surface of the multilayer ceramic capacitor 1.

[0021] In this regard, the multilayer ceramic capacitor to which the present invention is directed is not limited to a two-terminal type having a first external electrode 6 and a second external electrode 7 as shown in Fig. 1, but may be a multi-terminal type having three or more external electrodes. In this case, it is sufficient that the capacitor is configured so that a voltage is applied between two specific pairs of external electrodes selected from the three or more external electrodes, that is, between at least one first external electrode and at least one second external electrode, so that the first internal electrode is a positive electrode and the second internal electrode is a negative electrode.

[0022] The multilayer ceramic capacitor 1 has a second feature in that the metal compositions of the first internal electrode 4 and the second internal electrode 5 are selected as follows: the first internal electrode 4 serving as the positive electrode has a first metal composition containing Ni and Sn, and the second internal electrode 5 serving as the negative electrode has a second metal composition containing Ni. The second metal composition of the second internal electrode has a second characteristic that it contains Ni as a main component and at least one metal element selected from Au, Pt, Ir, Pd, Os, Ag, Rh, Ru, and Cu, which have a higher standard electrode potential than Ni, as an additive component. .

[0023] The selection of the metal composition of each of the first internal electrode 4 and the second internal electrode 5 is based on the following findings.

[0024] The mechanism of insulation degradation in general multilayer ceramic capacitors has not yet been elucidated, but it is known that the trigger is the negative electrode segregation of oxygen ions (positive electrode segregation of oxygen vacancies) caused by the application of voltage. Therefore, it is predicted that insulation degradation in multilayer ceramic capacitors can be suppressed by suppressing the negative electrode segregation of oxygen ions. One possible solution is to include elements whose oxides are stable in the positive electrode and elements whose oxides are unstable in the negative electrode. Based on this idea, it would be possible to suppress negative electrode segregation by causing a reduction reaction (release of oxygen ions) at the negative electrode.

[0025] More specifically, with regard to the metal composition of each of the first internal electrode 4 and the second internal electrode 5, a metal element whose valence is likely to increase (whose standard electrode potential is low) is used on the side of the first internal electrode 4, which serves as the positive electrode, and a metal element whose valence is likely to decrease (whose standard electrode potential is high) is used on the side of the second internal electrode 5, which serves as the negative electrode. The standard electrode potential is a value specific to an element; the lower the value, the more stable the oxide, and the higher the value, the more unstable the oxide.

[0026] That is, the second internal electrode 5 on the negative electrode side contains a metal element having a standard electrode potential higher than the standard electrode potential of the metal element of the first internal electrode 4 on the positive electrode side, as shown in Fig. 2. In Fig. 2, the standard electrode potential of the first metal composition of the first internal electrode 4 on the positive electrode side may be included in the range A, and the standard electrode potential of the second metal composition of the second internal electrode 5 on the negative electrode side may be included in the range B.

[0027] The standard electrode potentials of the metal elements that may be included in the metal composition of each of the internal electrodes 4 and 5 are, in order from lowest to highest, as follows: Ni is -0.26V, Sn is -0.14V, Cu is +0.34V, Ru is +0.46V, Rh is +0.76V, Ag is +0.8V, Os is +0.9V, Pd is +0.92V, Ir is +1.16V, Pt is +1.19V, Au is +1.52V.

[0028] The standard electrode potential of Ni contained in the first metal composition of the first internal electrode 4 is -0.26V, and the standard electrode potential of Sn is -0.14V, whereas the standard electrode potential of Ni contained in the second metal composition of the second internal electrode 5 is -0.26V. Here, Ni is easily passivated, i.e., in a non-oxidized state, and its standard electrode potential is -0.26V, but in reality, it can be considered to be approximately 0V. Therefore, when comparing the standard electrode potentials between the first internal electrode 4 and the second internal electrode 5, the standard electrode potential of Sn, which is -0.14V, is used for the first internal electrode 4, and the standard potential of approximately 0V due to the passivation of Ni is used for the second internal electrode 5.

[0029] Therefore, according to this embodiment, the standard electrode potential provided by the second internal electrode 5, which is the negative electrode, is higher than the standard electrode potential provided by the first internal electrode 4, which is the positive electrode, so that the oxidation-reduction reaction in the internal electrodes 4 and 5 is utilized to suppress the negative electrode segregation of oxygen ions (positive electrode segregation of oxygen vacancies) caused by voltage application. As a result, insulation deterioration of the multilayer ceramic capacitor 1 when voltage is applied can be suppressed, and therefore a multilayer ceramic capacitor 1 with excellent reliability can be obtained.

[0030] The second metal composition of the second internal electrode 5 may contain only Ni as described above, but it is preferable that the second metal composition contains Ni as the main component and contains at least one metal element selected from Au, Pt, Ir, Pd, Os, Ag, Rh, Ru, and Cu, which has a higher standard electrode potential than Ni, as an additive component. Au, Pt, Ir, Pd, Os, Ag, Rh, and Ru contained in the second metal composition are precious metals.

[0031] With regard to the metal composition of the internal electrodes 4 and 5, the term "main component" refers to the metal element having the largest content, more specifically, the metal element having a content of 50% or more.

[0032] In the above-described preferred embodiment, the standard electrode potential of Ni contained in the first metal composition of the first internal electrode 4 is −0.26 V, and the standard electrode potential of Sn is −0.14 V, whereas Au, Pt, Ir, Pd, Os, Ag, Rh, Ru and Cu which are added components in the second metal composition of the second internal electrode 5 all have a higher standard electrode potential than Sn.

[0033] Therefore, at least one of the metal elements Au, Pt, Ir, Pd, Os, Ag, Rh, Ru, and Cu added to the second metal composition of the second internal electrode 5, which is the negative electrode, can further cause a reduction reaction to occur in the second internal electrode 5, which is the negative electrode, and can further suppress the segregation of oxygen ions to the negative electrode.

[0034] As described above, the higher the standard electrode potential, the more unstable the oxide is. Therefore, the metal elements that may be included as additive components in the second metal composition of the second internal electrode 5 described above have a greater effect of suppressing the negative electrode segregation of oxygen ions in the following order of increasing standard electrode potential: Cu, Ru, Rh, Ag, Os, Pd, Ir, Pt, and Au.

[0035] Moreover, it is preferable that the first metal composition of the first internal electrode 4 does not contain a metal element having a standard electrode potential higher than Sn, because this makes it possible to advantageously maintain the relatively low standard electrode potential of the first metal composition.

[0036] In addition, since the first metal composition of the first internal electrode 4 and the second metal composition of the second internal electrode 5 both contain Ni, the melting point can be made higher than when the main component is, for example, Cu. Therefore, the first internal electrode 4 and the second internal electrode 5 can be made thinner, so that the number of laminations can be increased while maintaining the outer dimensions of the multilayer ceramic capacitor 1, and as a result, the obtained capacitance can be increased.

[0037] The Ni and Sn contained in the first metal composition of the first internal electrode 4 are contained in the conductive paste applied to the ceramic green sheet during the manufacturing process of the multilayer ceramic capacitor 1, but they may be contained in the conductive paste in advance in the form of an alloy or intermetallic compound containing Ni and Sn, or Ni and Sn may be contained in the conductive paste in separate forms. When the second metal composition of the second internal electrode 5 contains a plurality of metal elements, they may be contained in the conductive paste in advance in the form of an alloy or intermetallic compound containing a plurality of metal elements, or they may be contained in the conductive paste in the form of separate metal elements.

[0038] Furthermore, it is preferable that the Ni and Sn contained in the first metal composition of the first internal electrode 4 are alloyed with these multiple metal elements at the stage of the multilayer ceramic capacitor 1 as a product. Similarly, when the second metal composition of the second internal electrode 5 contains multiple metal elements, it is preferable that these multiple metal elements are alloyed with each other at the stage of the multilayer ceramic capacitor 1 as a product. [Explanation of symbols]

[0039] 1. Multilayer ceramic capacitors 2. Laminate 3 Dielectric Layer 4 1st internal electrode 5 Second internal electrode 6 1st external electrode 7 Second external electrode

Claims

[Claim 1] a laminate including a plurality of laminated dielectric layers made of ceramic and a plurality of internal electrodes respectively disposed along a plurality of interfaces between the dielectric layers; a plurality of external electrodes provided on an outer surface of the laminate and electrically connected to the internal electrodes; Equipped with the internal electrodes include a plurality of first internal electrodes and a plurality of second internal electrodes arranged alternately with respect to a stacking direction of the laminate, the external electrode includes a first external electrode electrically connected to the first internal electrode and a second external electrode electrically connected to the second internal electrode, The polarity is determined based on the direction of application of a voltage between the first external electrode and the second external electrode such that the first internal electrode is a positive electrode and the second internal electrode is a negative electrode. 、 the first internal electrode has a first metal composition including Ni and Sn; the second internal electrode has a second metal composition including Ni; The second metal composition of the second internal electrode contains Ni as a main component and at least one metal element selected from Au, Pt, Ir, Pd, Os, Ag, Rh, Ru, and Cu, which has a standard electrode potential higher than that of Ni, as an additive component; The first metal composition of the first internal electrode does not contain a metal element having a standard electrode potential higher than that of Sn. Multilayer ceramic capacitor.

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