# Patent

## Title
Laminated ceramic electronic component

## Abstract

Provided is a laminated ceramic electronic component which has excellent mechanical characteristics, internal electrode corrosion resistance, high degree of freedom in ceramic material design, low cost, low defective rate, and various properties. The laminated ceramic electronic component includes a laminate which has a plurality of laminated ceramic layers and internal electrodes formed along at a plurality of specific interface between the ceramic layers and having an Al/Ti alloy as a component; and an external electrode formed on the outer surface of the laminate. The Al/Ti ratio of the Al/Ti alloy is 91/9 or more.

## Background
This is a continuation of application Serial No. PCT/JP2011/052525, filed Feb. 7, 2011, the contents of which are incorporated herein by reference.


TECHNICAL FIELD
The present invention relates to a laminated ceramic electronic component, for example, a laminated ceramic capacitor, and more particularly relates to one including an internal electrode having an Al alloy as a component.
BACKGROUND ART
With reference to FIG. 1, a laminated ceramic electronic component according to the present invention using a laminated ceramic capacitor 1 as an example will be first described.
The laminated ceramic capacitor 1 includes a laminate 2 having a plurality of internal electrodes 4 and 5 formed along specific interfaces between a plurality of laminated dielectric ceramic layers 3.
First and second external electrodes 6 and 7 are formed at different locations on the outer surface of the laminate 2. In the laminated ceramic capacitor 1 shown in FIG. 1, first and second external electrodes 6 and 7 are formed on opposite end surfaces of the laminate 2. Internal electrodes 4 and 5 include a plurality of first internal electrodes 4 electrically connected to the first external electrode 6 and a plurality of second internal electrodes 5 electrically connected to the second external electrode 7, and the first and second internal electrodes 4 and 5 are arranged alternately with respect to the laminating direction.
Various metal elements are conceivable for the internal electrode of the laminated ceramic electronic component, but base metals are often considered for the purpose of cost reduction.
However, base metals are very easily oxidized when co-fired with a ceramic, and it has been necessary to have a reducing atmosphere during firing and precisely control the temperature and oxygen partial pressure conditions. As a result, material design has been considerably limited. In addition, there have been concerns of delamination resulting from an uneven stress associated with the co-firing, and so on.
In the case of using an internal electrode made of a base material alone, there has been concern about the corrosion resistance of the internal electrode if a ceramic laminate after being fired is exposed to a high-temperature and high-humidity environment.
Patent Document 1 discloses a laminated ceramic electronic component using a base metal alloy as an internal electrode material. Specifically, the base metal alloy is a Ni/Al alloy and a Ti/Al alloy.
PRIOR ART PATENT DOCUMENT
Patent Document 1: JP 6-84608 A
DISCLOSURE OF THE INVENTION
Problem to be Solved by the Invention
The firing atmosphere for the laminated ceramic electronic component in Patent Document 1 is a nitrogen atmosphere, and therefore a re-oxidation treatment of the ceramic material is required, so that the process is complicated.
Further, the laminated ceramic electronic component in Patent Document 1 has the problem that a heavy stress is applied due to influences of shrinkage behaviors during the temperature reduction in the firing process, and thus delamination easily occurs.
Thus, an object of the present invention is to provide a laminated ceramic electronic component including an internal electrode made of a base metal alloy, wherein mechanical troubles such as delamination are inhibited, and firing can be performed even in the air.
Means for Solving the Problem
The present invention is a laminated ceramic electronic component including: a laminate which has a plurality of laminated ceramic layers and a plurality of internal electrodes formed at specific interfaces between the ceramic layers and having an Al/Ti alloy as a component; and an external electrode formed on the outer surface of the laminate, wherein the Al/Ti ratio of the Al/Ti alloy is 91/9 or more.
Advantages of the Invention
According to the present invention, a laminated ceramic electronic component can be obtained in which occurrence of delamination is inhibited because stresses applied to ceramic layers from internal electrodes during firing are low. In addition, a fixed amount of Ti is contained in Al of the internal electrode to improve the corrosion resistance of the internal electrode, so that a laminated ceramic electronic component having high reliability even in a high-humidity environment can be obtained.
In addition, the laminated ceramic electronic component of the present invention is capable of being fired in the air although the internal electrode is made of a base metal, and therefore the degree of freedom in ceramic material design is improved. Accordingly, a laminated ceramic electronic component having various properties can be obtained.



BRIEF EXPLANATION OF DRAWING
FIG. 1 is a view showing a laminated ceramic capacitor that is an example of a laminated ceramic electronic component of the present invention.



BEST MODE FOR CARRYING OUT THE INVENTION
A laminated ceramic electronic component of the present invention has internal electrodes having an Al/Ti alloy as a main component. If the Al/Ti ratio is 91/9 or more, the stress concentration between ceramic layers and internal electrodes is relieved, so that delamination defects are effectively suppressed.
If the laminated ceramic electronic component of the present invention has an oxygen partial pressure of 1×10−4 MPa or more (including the pressure in the air), the surface part of the internal electrode, i.e. a site contacting the ceramic layer, may be constituted by a layer having Al2O3 as a main component. This results principally from oxidation of the surface of the Al internal electrode. This Al2O3 layer prevents electrode breakage of the Al internal electrode, and keeps the conductivity of the Al internal electrode satisfactory. This Al2O3 layer also has an effect of smoothing the Al internal electrode layer. For exhibiting these effects, the thickness of Al2O3 layer is preferably 0.25% or more of the thickness of the internal electrode.
If the thickness of the Al2O3 layer is more than 10% of the thickness of the internal electrode, Al2O3 constitutes 20% of the total thickness of the internal electrode layer, and the improvement of the conductivity is compromised. Accordingly, the thickness of Al2O3 layer is preferably 10% or less of the thickness of the internal electrode.
A method for producing the laminated ceramic electronic component of the present invention will now be described using a laminated ceramic capacitor as an example.
First, a ceramic raw material is prepared. The ceramic raw material is mixed with an organic binder component, as required in a solvent, and thereby formed into a ceramic slurry. By sheet-molding the ceramic slurry, a ceramic green sheet is obtained.
Next, an internal electrode having an Al/Ti alloy as a main component is formed on the ceramic green sheet. For achieving this, there are several methods, among which the method of screen-printing a conductive paste containing an Al/Ti alloy powder and an organic vehicle in a desired pattern is convenient. In addition, there are the method of transferring a metal foil and the method of forming an Al/Ti film while carrying out masking by a vacuum thin film formation method.
The ceramic green sheets and internal electrode layers are stacked in multiple layers, and brought into close contact with one another under pressure to thereby a raw laminate before firing.
The raw laminate is fired in a kiln under a predetermined atmosphere and temperature conditions. For example, if the oxygen partial pressure during firing is 1×10−4 MPa or more and the firing temperature is 600° C. or more, oxidation of the surface of the internal electrode may proceed to form an Al2O3 layer having a moderate thickness. If the firing temperature is 1,000° C. or less, electrode breakage of the internal electrode is easily effectively prevented. Concerning the oxygen partial pressure, atmospheric pressure is most preferable when considering convenience of the process.
If the temperature increasing rate from room temperature to the maximum firing temperature in the firing process is 100° C./minute or more, an Al2O3 layer is easily formed on the surface of the internal electrode more reliably even though various changes, such as a change in ceramic material composition, occur.
It is to be noted that Al has a melting point of about 660° C., but can be co-fired with a ceramic even at a temperature of 660° C. or more according to the production method of the present invention. This is ascribable to the Al2O3 layer formed on the surface of the Al internal electrode. Thus, a high degree of freedom is also provided for material composition design of the ceramic used, and a variety of applications can be covered.
It is to be noted that the ceramic composition in the laminated ceramic electronic component of the present invention is not particularly limited. A variety of materials can be applied within the bounds of not impairing the object of the present invention, such as barium titanate-based materials (including those substituted with Ca, Sr, Zr and the like), lead titanate-based or lead zirconate titanate-based materials, alumina-based glass ceramics, ferrites and transition element oxide-based semiconductor ceramics.
The laminated ceramic electronic component of the present invention is applicable not only to a laminated ceramic capacitor, but also to a variety of electronic components such as a laminated piezoelectric element, a laminated thermistor element, a laminated chip coil and a ceramic multi-layered substrate.
EXAMPLE
In this Example, the Al/Ti ratio in the internal electrode was changed, and effects thereof on delamination were examined. Three ceramic materials having different compositions were prepared.
First, powders of BaTiO3, Bi2O3 and CuO were prepared as a first ceramic material. These powders were mixed so as to satisfy the composition ratio described in “Material 1” in Table 1 to obtain a first ceramic raw material.
Similarly, a powder of (Pb0.88Bi0.12) (Ni1/2Nb1/2)0.15Ti0.45Zr0.40)O3 was prepared as a second ceramic material. This was the second ceramic raw material.
Similarly, powders of BaTiO3, Bi2O3 and SiO2 were prepared as a third ceramic material. These powders were mixed so as to satisfy the composition ratio described in “Material 3” in Table 1 to obtain a third ceramic raw material.
An ethanol-based organic solvent and a polyvinyl butyral-based binder were added to each of these ceramic raw materials, and the resulting mixture was mixed in a wet process by a ball mill to obtain a ceramic slurry. The ceramic slurry was sheet-molded to obtain a ceramic green sheet.
Al/Ti alloy powders with the Al/Ti ratio within a range of 99.9/0.1 to 90/10 as described in Table 1 was prepared. The alloy powders were mixed an acetate-based organic solvent and a cellulose-based binder to obtain an Al/Ti paste.
Next, an Al/Ti paste with the Al/Ti ratio within the range of 99.9/0.1 to 90/10 was coated on each of the three ceramic green sheets by screen printing to form an Al/Ti paste layer. Ceramic green sheets coated with the Al/Ti paste were laminated so as to be arranged alternately in terms of the side at which the Al/Ti paste layer was drawn, and brought into close contact with one another under pressure to obtain a raw laminate.
The raw laminate was heated in the air at 270° C. to remove the binder. Thereafter, the temperature was elevated at a temperature increase rate of 100° C./minute, and the laminate was fired in the air at the firing temperature shown in Table 2. An Ag paste containing a BaO—SiO2—BaO-based glass frit was coated on both end surfaces of the obtained laminate, and baked in the air at 600° C. to form an external electrode to be connected to the internal electrode.
The laminated ceramic electronic component thus obtained had a length of 2.0 mm, a width of 1.0 mm, a thickness of 1.0 mm, a thickness per ceramic layer of 15 μm, a thickness per internal electrode layer of 5 μm, and 30 effective layers contributing to an electrostatic capacity. The area of a portion confronted by the internal electrode per layer was 1.7×10−6 m2.
For the obtained samples, the electrostatic capacity and the dielectric loss (tan δ) were measured and it was found that it was practical as a laminated ceramic electronic component and there was no problem in conductivity of the internal electrode. A thin Al2O3 oxide film was formed on the surface of the internal electrode made of an Al/Ti alloy, and the smoothness and the continuity of the internal electrode were satisfactory.
Next, for 30 of each sample, the presence/absence of delamination was inspected by ultrasonic flaw detection. A sample in which any delamination could be observed at all was considered as a defective, and the number of such samples was shown in Table 1.











TABLE 1








Firing





Al/Ti
temperature
Number of


Material
Material composition
(atom)
[° C.]
defectives







1
90BaTiO3 + 8Bi2O3 + 2CuO
99.9/0.1
800
0/30



(mol %)
99/1
800
0/30




96/4
800
0/30




96/4
800
0/30




92/8
800
0/30




91/9
800
0/30




 80/10
800
5/30


2
(Pb0.88Bi0.12)((Ni1/2Nb1/2)0.15Ti0.45Ti0.45Zr0.40)O3
99.9/0.1
850
0/30




99/1
850
0/30




96/4
850
0/30




94/6
850
0/30




92/8
850
0/30




91/9
850
0/30




 90/10
850
5/30


3
50BaTiO3 + 25SiO2 + 25Bi2O3
99.9/0.1
750
0/30



(vol %)
99/1
750
0/30




96/4
750
0/30




94/6
750
0/30




92/8
750
0/30




91/9
750
0/30




 90/10
750
5/30









From the results in Table 1, the number of delamination defectives was 0 in those samples in which the Al/Ti ratio in the internal electrode satisfied 99.9/0.1 to 91/9 for the laminated ceramic capacitors using the three ceramic materials described above. On the other hand, for samples having an Al/Ti ratio of less than 91/9, a delamination defect occurred.
Industrial Applicability
A laminated ceramic electronic component of the present invention is applicable for a laminated ceramic capacitor, a laminated piezoelectric element, a laminated thermistor, a laminated chip coil, a ceramic multi-layered substrate, and the like.

## Claims

1. A laminated ceramic electronic component comprising a laminate which has a plurality of laminated ceramic layers and Al/Ti alloy-containing internal electrodes at a plurality of specific interfaces between the ceramic layers, wherein the Al/Ti atomic ratio in the Al/Ti alloy is 91/9 or more.

2. The laminated ceramic electronic component according to claim 1, wherein at least one internal electrode has a layer of Al2O3 on its surface.

3. The laminated ceramic electronic component according to claim 2, wherein the Al2O3 constitutes 0.25% to 10% of the thickness of the internal electrode.

4. The laminated ceramic electronic component according to claim 3, wherein the ceramic comprises a titanate, zirconate, glass ceramic, ferrite or transition element oxide ceramic.

5. The laminated ceramic electronic component according to claim 4, further comprising at least one external electrode on an outer surface of the laminate.

6. The laminated ceramic electronic component according to claim 3, further comprising at least one external electrode on an outer surface of the laminate.

7. The laminated ceramic electronic component according to claim 2, further comprising at least one external electrode on an outer surface of the laminate.

8. The laminated ceramic electronic component according to claim 1, further comprising at least one external electrode on an outer surface of the laminate.

9. The laminated ceramic electronic component according to claim 1, wherein the Al/Ti atomic ratio in the Al/Ti alloy is 92/1 to 99.9/0.1.

10. The laminated ceramic electronic component according to claim 9, wherein at least one internal electrode has a layer of Al2O3 on its surface.

11. The laminated ceramic electronic component according to claim 10, wherein the Al2O3 constitutes 0.25% to 10% of the thickness of the internal electrode.

12. The laminated ceramic electronic component according to claim 1, wherein the ceramic layer comprises a barium titanate-based perovskite compound, and the laminated ceramic electronic component is a laminated ceramic capacitor.

13. The laminated ceramic electronic component according to claim 12, further comprising at least one external electrode on an outer surface of the laminate.

14. The laminated ceramic electronic component according to claim 13, wherein at least one internal electrode has a layer of Al2O3 on its surface.

15. The laminated ceramic electronic component according to claim 14, wherein the Al2O3 constitutes 0.25% to 10% of the thickness of the internal electrode.

16. The laminated ceramic electronic component according to claim 1, wherein the ceramic layer comprises a lead zirconate titanate-based perovskite compound, and the laminated ceramic electronic component is a laminated piezoelectric element.

17. The laminated ceramic electronic component according to claim 16, further comprising at least one external electrode on an outer surface of the laminate.

18. The laminated ceramic electronic component according to claim 17, wherein at least one internal electrode has a layer of Al2O3 on its surface.

19. The laminated ceramic electronic component according to claim 18, wherein the Al2O3 constitutes 0.25% to 10% of the thickness of the internal electrode.