JPH08124789A - Manufacture of ceramic multilayered electronic component, and ceramic multilayered electronic component - Google Patents

Abstract

PURPOSE: To provide a method for obtaining a small-sized ceramic multilayered electronic component of high performance wherein the thickness of a ceramic layer between inner conductors can be reduced, and defect like delamination is hardly generated. CONSTITUTION: When a ceramic multilayered electronic component wherein a plurality of inner electrodes are formed in a ceramic sintering body is manufactured, a metallic film multilayered body 13 is obtained by stacking a plurality of metal films 5, 6, 10. The metallic film laminate 13 is baked and nitrided. Thereby a part of the metallic film multilayered body 13 is turned to metallic nitride ceramic and constitutes at least one part of the ceramic sintered body. Thus a ceramic multilayered board is manufactured.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a ceramic laminated electronic component having a plurality of internal conductors in a ceramic sintered body, and more particularly to a ceramic laminated electronic in which the steps for forming the ceramic sintered body and the internal conductor are improved. The present invention relates to a method of manufacturing a component.

INDUSTRIAL APPLICABILITY The present invention can be utilized in various ceramic laminated electronic component manufacturing methods such as a laminated capacitor, a laminated piezoelectric component, a laminated varistor, and a ceramic multilayer substrate.

[0003]

2. Description of the Related Art In recent years, with the miniaturization of electronic equipment, there has been a demand for miniaturization and high performance of all electronic components including ceramic laminated electronic components. An example of a conventional method for manufacturing a ceramic multilayer electronic component will be described taking a multilayer capacitor as an example.

In manufacturing a laminated capacitor, first, a mother ceramic green sheet is formed by a doctor blade method or the like on a support made of a synthetic resin film such as a polyethylene terephthalate film. Next, a conductive paste containing a metal such as a silver-palladium alloy or nickel is screen-printed on the mother ceramic green sheet to form an internal electrode having a predetermined pattern. Next, the mother ceramic green sheet having the internal electrode pattern formed thereon is peeled from the support, and a predetermined number of layers are laminated. Further, if necessary, plain ceramic green sheets on which internal electrodes are not printed are laminated on the upper and lower sides to obtain a raw ceramic laminated body.
Then, the green ceramic laminate is pressed in the thickness direction to press the ceramic green sheets together. Thereafter, the obtained mother laminated body is cut into chips of individual laminated capacitor units and fired to obtain a sintered body. Applying conductive paste to both end surfaces of the obtained sintered body,
By baking, an external electrode is formed and a multilayer capacitor is obtained.

In the multilayer capacitor, in order to achieve miniaturization and high capacity, it is required to reduce the thickness of the ceramic layer between the internal electrodes. That is, by reducing the thickness of the ceramic layer sandwiched between the internal electrodes,
The size and the capacity have been increased, and the capacity has been increased by reducing the thickness of the ceramic layer and increasing the number of laminated internal electrodes.

However, in the above-mentioned conventional method for manufacturing a multilayer capacitor, since the internal electrodes are formed by using the conductive paste, there is a problem that the ceramic green sheet swells / dissolves by the solvent contained in the conductive paste. there were. However, when a ceramic green sheet having a relatively large thickness is used as in the prior art, even if the surface layer portion of the ceramic green sheet swells to some extent, it does not cause a problem. However, if the thickness of the ceramic green sheet is reduced in order to achieve high performance and large capacity, the entire ceramic green sheet may swell and dissolve due to the solvent contained in the conductive paste. There was a limit to how thin the seat could be.

As a solution to the above problems, there has been proposed a method of forming internal electrodes by a metal film formed by a thin film forming method instead of a conductive paste (Japanese Patent Laid-Open No. 64-42809).

In this method, on the support film,
A metal film for internal electrodes is formed by a thin film forming method to obtain an internal electrode transfer material. Separately, a ceramic green sheet is formed on a support. After that, the internal electrodes supported by the support film are transferred onto the ceramic green sheets to obtain electrode-integrated ceramic green sheets. Further, the electrode-integrated ceramic green sheet is peeled off from the support, and the electrode-integrated ceramic green sheet is laminated by a transfer method to obtain a raw ceramic laminate.

[0009]

As described above, in the method of forming the internal electrodes by the metal film formed by the thin film forming method, the ceramic green sheet is not thinned because the ceramic green sheet is not swollen or dissolved. Is possible. However, this involves the work of forming the electrode-integrated ceramic green sheet on the support and then peeling the electrode-integrated ceramic green sheet from the support. Therefore, if the ceramic green sheet does not have a certain level of strength, there arises a problem that the ceramic green sheet is damaged when the electrode-integrated ceramic green sheet is peeled off. Therefore, even in the method of forming the internal electrodes by the thin film forming method, a ceramic green sheet having a certain thickness must be used, and in reality, it is very difficult to use a ceramic green sheet having a thickness of 2 μm or less. It was difficult.

On the other hand, although not yet known, a method of forming a ceramic green sheet on a stacking stage and transferring the internal electrodes to the ceramic green sheet to stack the ceramic green sheet has been considered. In this method, since the ceramic green sheet is not peeled off, it is possible to reduce the thickness of the ceramic green sheet. However, in this method, since the ceramic green sheets are laminated while being formed, it takes a long time to obtain the ceramic laminate, and the productivity is reduced.

Further, when the internal electrode is formed of a metal film formed by a thin film forming method, the surface smoothness of the internal electrode is increased. Therefore, there is a problem that the bonding force between the ceramic layer and the internal electrode becomes small, and the delamination phenomenon called delamination tends to occur in the finally obtained sintered body.

When a functional element such as a resistance element is formed by the internal conductor, the volume resistivity of the metal film formed by the thin film forming method becomes too low. Therefore, in order to realize a desired resistance value, it is necessary to reduce the cross-sectional area of the internal conductor that constitutes the resistance element and increase the length of the element. That is, if a metal film formed by a thin film forming method is used as it is for forming a functional element such as a resistance element, it may not be possible to obtain a ceramic laminated electronic component having high performance regardless of its size.

An object of the present invention is to solve the above-mentioned drawbacks of the conventional method for manufacturing a ceramic laminated electronic component, to reduce the thickness of the ceramic layer between the internal conductors, and to prevent defects such as delamination from occurring. , To provide a method for manufacturing a small-sized high-performance ceramic laminated electronic component.

[0014]

The first invention of the present application is a method for manufacturing a ceramic laminated electronic component in which a plurality of internal conductors are formed in a ceramic sintered body, wherein a plurality of metal films are laminated to form a metal film. A step of obtaining a laminate, a firing step of firing the metal film laminate, a nitriding treatment of the metal film laminate,
And a nitriding step of forming a ceramic sintered body by using a part of the metal film laminate as metal nitride ceramics.

That is, in the first invention of the present application, a part of the metal film laminate is made into a metal nitride ceramic by nitriding the metal film laminate, thereby forming a ceramic sintered body. To do.

In the above-mentioned nitriding step, a part of the metal film laminate may be a part constituting the ceramic sintered body using metal nitride ceramics, and the remaining part may be an internal conductor made of metal, or the metal film laminate is A part of the body may be nitrided to form a ceramic sintered body as metal nitride ceramics, and at least a part of the remaining portion may be nitrided to form an internal conductor made of metal nitride.

That is, except for the portion constituting the ceramic sintered body, the inner conductor may be made of metal, or the inner conductor may be made of metal nitride. Further, the inner conductor may be composed of both metal and metal nitride.

The internal conductor in the present specification is not limited to an electrode, but includes a conductor having a relatively low conductivity which functions as, for example, a resistance element. A second invention of the present application is a method of manufacturing a ceramic laminated electronic component in which a plurality of internal conductors are formed in a ceramic sintered body, the step of obtaining a laminated body of a plurality of preformed metal films and ceramics, A ceramic multi-layer electronic device, comprising: a step of firing the laminated body; and a nitriding step of nitriding the metal film to form a ceramic sintered body by using a part of the metal film as metal nitride ceramics. A method of manufacturing a component is provided.

That is, in the second invention, as a laminate,
A laminated body of a plurality of preformed metal films and ceramics is prepared. Then, by nitriding the metal film in the above-mentioned laminated body, a part of the metal film is made into a metal nitride ceramic as in the case of the first invention to form a part of the ceramic sintered body.

Also in the second invention, in the nitriding step, a part of the metal film is made of metal nitride ceramics to form a part of the ceramic sintered body, and the remaining part is made of an internal conductor made of the metal film. Alternatively, a part of the metal film may be a metal nitride ceramic to form a part of the ceramic sintered body, and at least a part of the remaining part may be an internal conductor made of a metal nitride. Also in the second aspect of the invention, the inner conductor may be made of both metal and metal nitride.

The nitriding step in the first and second inventions may be performed before the firing step, in the same heating step as the firing step, or after the firing step. .

The firing process in the first and second inventions does not mean a firing process of ceramics in a narrow sense, but heat treatment promotes grain growth of ceramics or metals to increase the bonding strength between grains in each layer. The heat treatment for increasing the temperature is widely included.

As the metal film in the first and second inventions, it is preferable to use a metal film formed by a known thin film forming method such as vapor deposition, ion plating, sputtering and plating. The metal film formed by the thin film forming method can be made considerably thin. Therefore, when the metal nitride ceramics are formed in the nitriding step to form the ceramic portion, the thickness of the ceramic layer between the internal conductors can be made very thin.

The metal film may contain a ceramic or an organic substance inside, and may be a porous metal film. When a metal film containing an organic substance is used as the metal film,
Organic substances are scattered during the firing process, and as a result, the organic metal has a structure similar to that of the porous metal film. Even when the metal film is formed of a porous metal film or contains an organic substance as described above, the voids disappear eventually due to expansion of the metal film during firing. Moreover, since the expansion is absorbed by the disappearance of the holes, the dimensional change of the metal film before and after firing can be reduced, and the internal conductor can be formed with high accuracy. Many holes are formed in the metal film.

The ceramic laminated electronic component of the present invention is obtained by the above first and second inventions.
In the ceramic laminated electronic component obtained by the invention, the ceramic sintered body has a ceramic portion made of metal nitride ceramics. However, in the second invention, a ceramic sintered body is constituted by the ceramic portion made of the above metal nitride ceramics and the ceramics first laminated with the metal film.

[0026]

In the method for manufacturing a ceramic laminated electronic component according to the first aspect of the present invention, a part of the metal film laminated body is made of metal nitride ceramics, and a ceramic sintered body is constituted by this. Therefore, since the ceramic layer in the inner conductor can be formed by the ceramic layer obtained by nitriding the metal film, even if the thickness of the ceramic layer between the inner conductors is reduced, the ceramic laminated electronic component has high reliability. It can be manufactured with.

Accordingly, it is possible to provide a small-sized and high-performance ceramic laminated electronic component in which the thickness of the ceramic layer between the inner conductors is thin. In the nitriding step,
A ceramic sintered body is formed by using a part of the metal film laminated body as metal nitride ceramics, and the remaining part of the metal film laminated body is made into an internal conductor made of metal, or at least part of the remaining part is nitrided. By forming the internal conductor with metal nitride, not only the ceramic sintered body portion but also the internal conductor can be formed by utilizing a part of the metal film laminate.

Therefore, only by carrying out the nitriding step and the firing step, it is possible to easily and easily obtain a ceramic sintered body in which a plurality of internal conductors are laminated via ceramic layers.

In the second invention of the present application, a laminated body of a plurality of preformed metal films and ceramics is used, and in the nitriding step, a part of the metal film is made into metal nitride ceramics and ceramic sintered. Make up a part of the body. Therefore, the ceramic sintered body is composed of the ceramic which is first laminated with the metal film and the metal nitride ceramic. Therefore, since a part of the plurality of metal films constitutes a ceramic part, the thickness of the ceramic layer between the inner conductors can be made extremely thin by nitriding the metal film between the inner conductors into ceramics. Therefore, a compact and high-performance ceramic laminated electronic component can be provided.

Also in the second invention, in the nitriding step,
A part of the metal film may be a metal nitride ceramic to form a part of the sintered body, and the remaining part may be an internal conductor made of a metal film or an internal conductor made of a metal nitride. By going through the firing step and the nitriding step, it is possible to easily obtain a ceramic sintered body in which a plurality of internal conductors are laminated via ceramic layers.

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be clarified by describing embodiments with reference to the drawings.

Example 1 First, the AlN substrate 1 shown in FIG. 1 was prepared. Next, Al
On the N substrate 1, an acrylic adhesive is used as an adhesive that does not affect the characteristics of the finished product.
The Pd alloy thin film 2 was adhered so as to have a predetermined pattern. Furthermore, as shown in FIG. 1, Ag-Pd alloy thin film 2
The aluminum films 3, 3 and Ta having the same thickness are provided in the area between
The metal film 4 was similarly adhered.

An aluminum film 6 having a thickness of 0.5 μm was adhered on the entire surface of the one-layer metal film 5 formed as described above. Next, as shown in FIG. 2, the Ag—Pd alloy films 7 and 7 were adhered on the aluminum film 6 in the same manner as described above so as to form a predetermined pattern. Further, the aluminum films 8 and 8 were adhered to the region between the Ag—Pd alloy films 7 and 7, and the Ta film 9 was similarly adhered. An aluminum film 11 having a thickness of 0.5 μm was adhered on the metal film 10 thus obtained. Furthermore, a sintering agent-containing AlN green sheet 12 having a thickness of 10 μm is formed on the aluminum film 11.
Was pressure-bonded to obtain a laminated body 13.

The obtained laminated body was subjected to 130 ° C. in a nitrogen atmosphere.
Heat treatment was performed for 2 hours at a temperature of 0 ° C. As a result, shown in FIG.
A ceramic sintered body was obtained. With the ceramic sintered body 14
Is the same as the AlN substrate 1 described above.
The integrated AlN layer is integrated into a ceramic
The box portion 14a is configured. Also, ceramics
The internal electrode 2 made of an Ag-Pd alloy is provided in the portion 14a.
A, 2A, 2A, 7A, 7A are formed. Also,
Ta film having a thickness of 0.5 μm is obtained by nitriding the Ta films 4 and 9. ₂N?
Functional inner conductors 4A and 9A consisting of a resistive element
Has been done.

As described above, the ceramic multilayer substrate in which the functional inner conductors 4A and 9A as the resistance element and the inner electrodes 2A, 2A, 2A, 2A, 7A and 7A are formed in the ceramic sintered body 14 are formed. Is configured. Here, the thickness of the ceramic layer 14b between the functional inner conductors 4A and 9A is 0.5 μm because it is formed by the ceramic portion formed by nitriding the aluminum film 6.
m. That is, it is possible to obtain a ceramic multilayer substrate having a very small thickness between the inner conductors.

Example 2 First, the alumina substrate 21 shown in FIG. 4 is prepared. A 50 μm-thick Si film 22 was bonded onto the alumina substrate 21 using a commercially available foaming adhesive as a type of adhesive that loses its tackiness when the temperature exceeds a predetermined temperature (80 ° C. in this embodiment).

On the Si film 22, an acrylic adhesive is used as an adhesive that does not affect the characteristics of the finished product and has a thickness of 0.
The 5 μm Cr films 23, 23, 23 were adhered. Similarly,
Si films 24, 24, 24 having the same thickness were adhered to the regions between the Cr films 23, 23, 23. Further, the Si film 26 having a thickness of 0.5 μm was adhered on the entire surface of the metal film 25 obtained as described above.

The above steps are repeated 20 times so that the pattern of the Cr film is at a predetermined position, but the 20th S
The i entire surface film had a thickness of 50 μm to obtain a laminated body. Thereafter, the alumina substrate 21 shown in FIG. 4 is peeled off from the laminate obtained by heating to a temperature of 80 ° C. or higher,
A laminated body 27 shown in FIG.

Next, the laminate 27 was heat-treated at a temperature of 300 to 800 ° C. in a nitriding atmosphere (in nitrogen gas) to carry out a nitriding step. Further, the laminated body 27,
Cut into individual multilayer capacitor unit multilayer chips and
Firing was performed at a temperature of 200 to 1300 ° C to obtain a sintered body. External electrodes were added to the obtained sintered body to obtain a multilayer capacitor 28 shown in FIG.

When the inside of the sintered body was examined,
It was confirmed that the Si films 22, 24, 24, 24, 26 were changed to Si ₃ N ₄ , that is, they were nitride ceramics. It was also confirmed that the surface of the Cr film was changed to CrN or Cr ₂ N, while the inside of the Cr film remained Cr.

In the multilayer capacitor 28, external electrodes 30a and 30b are formed on both end surfaces of the sintered body 29. Further, in the sintered body 29, 20 layers of the internal electrodes 23A derived from the above-described Cr film are laminated via a ceramic layer made of Si ₃ N ₄ .

In the multilayer capacitor 28, as described above,
The ceramic layer between the internal electrodes 23A is the Si film 2 described above.
6 is composed of a ceramic layer which is made into a ceramic, and the thickness of this ceramic layer is about 0.4 μm, the thickness of the ceramic layer between the internal electrodes is very thin as compared with the conventional multilayer capacitor. .

Example 3 A laminated body 27 is obtained in the same manner as in Example 2, and the laminated body 27 is cut in the thickness direction so as to be a chip of each laminated capacitor unit, and a laminated body chip of each laminated capacitor unit. Got This laminated body chip was heat-treated at a temperature of 1200 ° C. in a nitriding atmosphere to simultaneously perform nitriding treatment and firing. Thereafter, external electrodes were added to the obtained sintered body in the same manner as in Example 2 to produce a multilayer capacitor.

Also in the multilayer capacitor obtained in Example 3, the sintered body is composed of Si ₃ N ₄ ceramics, and the thickness of the ceramic layer between the internal electrodes is about 0.4.
It was confirmed that the thickness was extremely thin at μm.

Example 4 The laminated body 27 prepared in Example 2 was cut into individual multilayer capacitor unit chips, and the obtained laminated body chips were heat-treated at a temperature of 800 ° C. in a reducing atmosphere to form a metal. The film was baked. Thereafter, the obtained sintered body was heat-treated at a temperature of 300 to 500 ° C. in a nitriding atmosphere to carry out a nitriding step. Thereafter, external electrodes were formed on both end faces of the sintered body to produce a multilayer capacitor.

In this example, however, an Ag film was used instead of Cr as the metal material for forming the internal electrodes. Also in this example, it was confirmed that the thickness of the ceramic layer made of Ag between the internal electrodes was very thin, about 0.4 μm. Thus, even when the nitriding step is performed after firing the laminated body, a laminated capacitor having a thin ceramic layer between internal electrodes can be stably obtained as in the second and third embodiments. It was

When the multilayer capacitors obtained in Examples 2 to 4 were examined, it was confirmed that delamination did not occur on the outer surface of the sintered body in any case. In the case of this embodiment, the firing is 800 ° C. and the nitriding process is 5
Since it can be performed at 00 ° C. or lower, Ag having a low melting point can be used for the internal electrodes. In Examples 1 to 4, the metal films were adhered to each other by using an adhesive when obtaining the metal film laminate, but the metal films may be laminated by another method.

Example 5 As shown in FIG. 7A, a 1 μm thick Cr film 42, 42 is formed on an alumina substrate 41 by using an acrylic adhesive as an adhesive that does not affect the characteristics of the finished product. Glued.

Next, as shown in FIG. 7B, the Cr film 4 is formed.
In the area where 2 is not provided, the Al film 43 of the same thickness,
43 and 43 were adhered in the same manner. In this way, the metal film 45 was formed.

Further, a thickness of 1 μm is formed on the metal film 45.
The Al film 46 was adhered using the above adhesive which does not affect the characteristics of the finished product. Next, as shown in (a), a Cr film 47 having a thickness of 1 μm was similarly adhered on the Al film 46.

After that, it was formed on the alumina substrate 41.
The laminated body 48 is supported by the alumina substrate 41.
Also, heat in a nitrogen atmosphere at 600 ° C to 900 ° C for 4 hours.
Processed, nitriding and firing steps were implemented. That conclusion
As a result, on the alumina substrate 41, Al films 43, 43, 43,
Ceramic composed of AlN formed by nitriding 46
A sintered body was formed in which the metal parts were integrated. Also, sintering
When the inside of the body was examined, it was found that the Cr films 42 and 42 were CrN.
₂The same applies to the Cr film 47 on the surface.
Also CrN₂It was confirmed to have changed to. Follow
In the ceramic multilayer substrate 49 shown in FIG.
Is the ceramic layer 49a composed of the Lumina substrate 41 and AlN?
In a substrate made of a ceramic sintered body formed from
N₂Embedded resistors 42A, 42A made of
And is also CrN on the surface ₂Resistor consisting of
47A is formed. In addition, the ceramic multilayer substrate 4
In 9, no delamination was observed.

Example 6 First, as shown in FIG. 9A, an alumina substrate 51 is prepared. Next, a 50 μm-thick Si film 52 was adhered to the entire surface of the alumina substrate 51 using a foaming adhesive that loses its tackiness when heated to a temperature of 70 ° C. or higher (FIG. 1B).

Next, the Ag—Pd alloy films 53, 53, 53 having a thickness of 0.5 μm and formed separately on the Si film 52 in advance.
Was bonded so as to form a predetermined pattern using an acrylic adhesive that does not affect the properties of the finished product.

Next, as shown in FIG. 1C, Ag-P
In a region between the d films 53, a similar adhesive is used, and the thickness is 0.
A 5 μm Si film 54 was adhered. Further, on the entire surface of the metal film 55 obtained as described above, S having a thickness of 0.5 μm is formed.
The i film 56 was adhered in the same manner.

The above metal film laminating step was repeated 20 times so as to have a predetermined laminated structure, but the thickness of the 20th Si film was 50 μm. After the above laminated body was formed on the alumina substrate 51, the whole was heated to a temperature of 70 ° C., and the space between the alumina substrate 51 and the first-layer Si film 52 was peeled off to obtain a laminated body.

Next, the nitriding step was carried out by heating the obtained laminated body at a temperature of 200 to 300 ° C. in a nitriding atmosphere to obtain a laminated body 57 shown in FIG. In the laminated body 57, a ceramic portion 54A made of Si ₃ N ₄ formed by nitriding the Si film is formed around the region where the Ag—Pd films 53, 53, 53 are formed. Further, the Si film 56 is nitrided, and similarly Si ₃
A ceramic layer 56A having a composition of N ₄ is formed.

This laminated body 57 was cut in the thickness direction so as to have a size of each laminated capacitor unit, and a laminated body raw chip was obtained. The obtained laminated body raw chip is 1000 to 120
Firing was performed at a temperature of 0 to obtain a sintered body 58 shown in a sectional view in FIG. In the sintered body 58, the internal electrodes 53A made of an Ag—Pd alloy are laminated via a ceramic layer made of Si ₃ N ₄ . External electrodes were provided on both end faces of this sintered body 58 to obtain a multilayer capacitor. In this multilayer capacitor, the thickness of the ceramic layer between the internal electrodes 53A and 53A is set to Si ₃ N ₄ derived from the Si film 56.
It was about 0.4 μm as determined by the layer.

Example 7 The laminated body before nitriding prepared in Example 6 was cut in the thickness direction so as to be a laminated body of each laminated capacitor unit, and a laminated body raw chip was obtained. By maintaining the obtained laminated green chip at a temperature of 1200 ° C. for 4 hours in a nitriding atmosphere, a nitriding step and a firing step were performed to obtain a sintered body. Using the obtained sintered body, a multilayer capacitor was produced in the same manner as in Example 6. In the obtained multilayer capacitor, as in Example 6, the thickness of the ceramic layer of the internal electrode was 0.4 μm.

Example 8 The multilayer body before nitriding prepared in Example 6 was cut in the thickness direction so as to have a size of each multilayer capacitor unit, and a multilayer green chip was obtained. A firing process was performed by maintaining the obtained laminated green chip at a temperature of 800 ° C. for 2 hours in a reducing atmosphere to sinter the metal films. Thereafter, the nitriding step was performed by maintaining the temperature at 300 ° C. for 2 hours in the nitriding atmosphere. In the obtained sintered body,
External electrodes were formed in the same manner as in Example 6 to produce a multilayer capacitor. Also in the multilayer capacitor obtained in this example, the thickness of the ceramic layer between the internal electrodes was 0.4 μm.
Met.

In the eighth embodiment, the heat treatment is 80
Since it can be performed at 0 ° C. or lower, an Ag film having the same thickness was used instead of the Ag—Pd film 53. When the characteristics of the multilayer capacitors manufactured in Examples 6 to 8 were measured, they showed the electrical characteristics as designed. Moreover, delamination was not observed in the sintered body.

Therefore, by nitriding a part or all of the metal film to form the ceramic sintered body portion, it is possible to obtain a laminated capacitor in which defects such as delamination are unlikely to occur and which has a small thickness between internal electrodes. I understand.

Further, as is clear from Example 8, since it was usually necessary to perform firing at a temperature of 1200 ° C. or higher, even when Pd was added to Ag as the internal electrode material, In the method of the present invention, since it is not necessary to perform firing at such a high temperature, it is possible to use an internal electrode made of only Ag, and it is possible to reduce the cost.

Example 9 First, an alumina substrate 61 shown in FIG. 12A is prepared. Then, on the alumina substrate 61, an Al adhesive 62 having a thickness of 1 μm was adhered using an acrylic adhesive as an adhesive that does not affect the characteristics of the finished product.

Next, as shown in FIG. 12B, the thickness 1
The μm Ag films 63 and 64 were adhered by the same method. Further, the Al films 65 to 67 having the same thickness are replaced by the Ag film 6 described above.
It adhere | attached between 3,64 by the same method. As described above, the metal film 68 was laminated on the Al film 62.

Further, an Al film 69 having a thickness of 1 μm was adhered on the entire surface of the metal film 68 by the same method as described above.
Next, a nitriding step and a firing step were performed by maintaining the temperature at 600 ° C. to 900 ° C. in a nitrogen atmosphere for 4 hours. As shown in FIG. 13B, in the obtained multilayer substrate 70, the Al film 6 is formed on the alumina substrate 61.
A structure was obtained in which the AlN ceramic layer 71 formed by firing 2,65 to 67,69 was integrated, and the Ag films 63 and 64 were embedded in the ceramic layer 71.

In the ceramic multilayer substrate 70, the thickness is 1 μm
It is understood that since the ceramic layer 71 made of AlN having the Ag films 63 and 64 and having a thickness of 1 μm is formed, the thickness of the ceramic layer of the ceramic multilayer substrate having the internal conductor can be made extremely thin. Further, no delamination was observed between the alumina substrate 61 and the ceramic layer 71.

Example 10 In the same manner as in Example 6, a laminated body composed of a metal film made of an Ag—Pd alloy and a Si metal film was formed. However, in Example 10, the porosity was about 30 as the Si metal film.
%, A Si film having a large number of through holes was used. Using the thus obtained laminated body, a laminated capacitor was produced in the same manner as in Example 6.

In the multilayer capacitor obtained in Example 10, the size of the laminated body before the heat treatment and the size of the sintered body after the heat treatment may be because the expansion of Si in the nitriding step and the contraction due to the disappearance of the voids cancel each other out. And, almost no change was seen.

Therefore, as described above, when the porous metal film is used, the expansion of the metal at the time of nitriding can be offset by the contraction due to the disappearance of the holes, so that a ceramic sintered body having a stable dimension can be obtained. As a result, it can be seen that a ceramic laminated electronic component having excellent dimensional accuracy can be provided.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a state in which a metal film is laminated and formed on an AlN substrate in Example 1.

FIG. 2 is a cross-sectional view showing a state in which a laminated metal film and an AlN green sheet are laminated on an AlN substrate in Example 1.

FIG. 3 is a sectional view showing a sintered body obtained in Example 1.

FIG. 4 is a cross-sectional view showing a state in which a metal film is laminated and formed on an AlN substrate in Example 2.

FIG. 5 is a cross-sectional view showing a metal film laminated body prepared in Example 2.

6 is a partially cutaway perspective view showing the structure of the multilayer capacitor obtained in Example 2. FIG.

7 (a) to 7 (c) are cross-sectional views showing a state where a metal film is formed on an alumina substrate in Example 5, and a cross-section showing a state where a two-layer metal film is formed on the alumina substrate. The figure and the sectional view showing the state where three layers of metal films were formed on an alumina substrate.

8A and 8B are cross-sectional views showing a laminated body and a sintered body prepared in Example 5, respectively.

9A to 9C are cross-sectional views showing an alumina substrate prepared in Example 6, a state in which a metal film is formed on the alumina substrate and a state in which a laminated metal film is formed on the alumina substrate, respectively. Fig.

FIG. 10 is a cross-sectional view showing a laminated body prepared in Example 6.

FIG. 11 is a cross-sectional view showing a sintered body obtained in Example 6.

12A and 12B are a cross-sectional view showing a structure in which an Al film is adhered on the alumina substrate prepared in Example 9 and a cross-sectional view showing a state in which a laminated metal film is formed on the alumina substrate, respectively. Fig.

13A and 13B are a cross-sectional view showing a state in which a laminated body is formed on an alumina substrate and a cross-sectional view showing the obtained ceramic multilayer substrate, respectively.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... AlN substrate 2 ... Ag-Pd alloy thin film 3 ... Aluminum thin film 4 ... Ta metal film 5 ... Metal film 6 ... Aluminum film 7,7 ... Ag-Pd alloy film 8 ... Aluminum film 9 ... Ta film 10 ... Metal film 11 ... Aluminum film 12 ... AlN green sheet 13 ... Layered body 14 ... Ceramic sintered body 4A, 9A ... Functional inner conductor 21 ... AlN substrate 22 ... Si film 23 ... Cr film 24 ... Si film 25 ... Metal film 26 ... Si film 27 ... Laminated body 28 ... Laminated capacitor 29 ... Sintered body 23A ... Internal electrode 41 ... Alumina substrate 42 ... Cr film 43 ... Al film 46 ... Al film 47 ... Cr film 48 ... Laminated body 49 ... Ceramic multilayer substrate 43A ... Internal electrode 51 ... Alumina substrate 52 ... Si film 53 ... Ag-Pd alloy film 53A ... Internal electrode 54 ... Si film 55 ... Metal film 56 ... Si film 57 ... Laminated body 8 ... sintered body 61 ... alumina substrate 62 ... Al film 63, 64 ... Ag film 65～67,69 ... Al film 65 ... metal film 70 ... ceramic multilayer substrate 71 ... ceramic layer

Claims (16)

[Claims] 1. A method of manufacturing a ceramic laminated electronic component, wherein a plurality of internal conductors are formed in a ceramic sintered body, the method comprising: laminating a plurality of metal films to obtain a metal film laminated body; A ceramic comprising: a firing step of firing a body; and a nitriding step of nitriding the metal film laminate to form a ceramic sintered body by using a part of the metal film laminate as a metal nitride ceramic. Manufacturing method of laminated electronic component. 2. The method for producing a ceramic laminated electronic component according to claim 1, wherein in the nitriding step, a part of the metal film laminate is made of metal nitride ceramics and the remaining part is made of an internal conductor made of metal. 3. In the nitriding step, a part of the metal film laminate is nitrided to be a metal nitride ceramic, and at least a part of the remaining part is nitrided to be an internal conductor made of metal nitride. 1. The method for manufacturing a ceramic laminated electronic component according to 1. 4. A method of manufacturing a ceramic laminated electronic component, wherein a plurality of internal conductors are formed in a ceramic sintered body, the method comprising: obtaining a laminate of a plurality of preformed metal films and ceramics; A ceramic laminated electronic component, comprising: a step of firing a body; and a step of nitriding the metal film to form a ceramic sintered body by using a part of the metal film as a metal nitride ceramic. Production method. 5. The method for manufacturing a ceramic laminated electronic component according to claim 4, wherein in the nitriding step, a part of the metal film is made of metal nitride ceramics and the remaining part is made of an internal conductor made of the metal film. 6. The ceramic multilayer electronic component according to claim 4, wherein in the nitriding step, a part of the metal film is made of metal nitride ceramics and at least a part of the remaining part is made of an inner conductor made of metal nitride. Manufacturing method. 7. The method for manufacturing a ceramic laminated electronic component according to claim 1, wherein the nitriding step is performed before the firing step. 8. The method for manufacturing a ceramic laminated electronic component according to claim 1, wherein the nitriding step is performed in the same heating step as the firing step. 9. The method for manufacturing a ceramic laminated electronic component according to claim 1, wherein the nitriding step is performed after the firing step. 10. The method for manufacturing a ceramic laminated electronic component according to claim 1, wherein the metal film is formed by a thin film forming method. 11. The method for manufacturing a ceramic laminated electronic component according to claim 1, wherein the metal film contains a ceramic or an organic substance therein. 12. The method for manufacturing a ceramic laminated electronic component according to claim 1, wherein the metal film is a porous metal film. 13. A ceramic laminated electronic component manufactured by the method for manufacturing a ceramic laminated electronic component according to claim 1, wherein the ceramic sintered body has a ceramic portion made of metal nitride ceramics. parts. 14. The ceramic laminated electronic component according to claim 13, wherein the sintered body has a metal nitride ceramic portion and an internal conductor portion made of metal nitride. 15. A ceramic laminated electronic component obtained by the method for producing a ceramic laminated electronic component according to claim 4, wherein the ceramic sintered body has a ceramic portion made of a metal film nitride ceramics. Electronic components. 16. The ceramic laminated electronic component according to claim 15, wherein the sintered body has a ceramic portion made of metal nitride ceramics and an internal conductor made of metal nitride.