JPH04284612A - Composite laminated component - Google Patents

Abstract

PURPOSE:To restrain that a metal such as Cu, Zn or the like and a low-resistance oxide such as Cu2O, Zn2O or the like are precipitated locally at the bonding interface between a ceramic magnetic layer and a ceramic dielectric layer and to obtain a composite laminated component whose circuit resistance is high by a method wherein, after the bonding interface between the ceramic magnetic layer and the ceramic dielectric layer has been formed to be a recessed and protruding shape, the layers are fired. CONSTITUTION:A capacitor chip body 2 constituted by laminating ceramic dielectric layers 21 and internal electrode layers 25 and an inductor chip body 3 constituted by laminating ceramic magnetic layers 31 and internal conductors 35 are united; external electrodes 51 are formed on the surface. Thereby, an LC composite component 1 is formed. At this time, the surface closest to the side of the capacitor chip body 2 out of the ceramic magnetic layers 31 and/or the surface closest to the side of the inductor chip body 3 out of the ceramic dielectric layers 21 are formed so as to be recessed and protruding; after that, the component is fired. Thereby, it is possible to restrain that Cu or Cu oxide and Zn or a Zn oxide or the like are precipitated locally at their interface, and it is possible to prevent that a layer whose electric resistance is low is formed.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to composite laminated parts such as LC composite parts.

0002

[Prior Art] A multilayer ceramic LC composite component includes a capacitor chip body composed of a laminated ceramic dielectric layer and an internal electrode layer, and an inductor chip body composed of a laminated ceramic magnetic layer and an internal conductor. It is integrally formed with.

[0003] Such composite laminated parts are often used in various electronic devices because of their small volume, high robustness, and high reliability.

These parts, such as LC composite parts, are usually produced by laminating paste for internal conductors, paste for magnetic layers, paste for dielectric layers, and paste for internal electrode layers using thick film technology, and then firing the resulting product. The external electrode paste is printed or transferred onto the surface of the sintered body, and then fired. In this case, the magnetic material used for the magnetic layer is Ni-
Cu-Zn ferrite is commonly used.

However, as a magnetic material, Ni-Cu-Z
It was found that when n-ferrite and Ni-Zn ferrite were used, the circuit resistance was significantly lower than expected.

[0006] The inventors of the present invention investigated this phenomenon and found that during firing or baking the external electrodes, the bonding interface between the ceramic magnetic layer of the inductor chip body and the ceramic dielectric layer of the capacitor chip body. It was found that Cu, Cu oxide, Zn, Zn oxide, etc. were precipitated to form a layer with low electrical resistance, and as a result, the circuit resistance of the component was significantly reduced.

[0007] In order to solve such problems, a bonding interface between the ceramic magnetic layer and the ceramic dielectric layer,
For example, an intermediate layer such as non-magnetic ferrite is provided, and Cu, Z
It is possible to prevent the precipitation of n and the like. Although such an intermediate layer reduces the amount of these precipitates, it cannot completely prevent local precipitation at the bonding interface. For this reason,
The circuit resistance of the component is not improved satisfactorily.

[0008]

[Problems to be Solved by the Invention] An object of the present invention is to prevent the localization of metals such as Cu, Zn, Cu2O, and Zn2O or oxides with low resistance at the bonding interface between a ceramic magnetic layer and a ceramic dielectric layer. The object of the present invention is to provide a composite laminated component that suppresses precipitation and has high circuit resistance.

[0009]

[Means for Solving the Problems] Such objects are achieved by the present invention as described in (1) to (10) below. (1) A composite multilayer component that integrally includes a capacitor chip body formed by laminating a ceramic dielectric layer and an internal electrode layer, and an inductor chip body formed by laminating a ceramic magnetic layer and an internal conductor. The ceramic magnetic layer is made of Ni-Cu-Zn ferrite and/or N
A composite containing i-Zn ferrite, characterized in that it is fired after forming irregularities on the surface of the ceramic magnetic layer closest to the capacitor chip body and/or the surface of the ceramic dielectric layer closest to the inductor chip body. Laminated parts. (2) The composite laminate component according to (1) above, wherein the height of the convex portion of the unevenness is 3 to 30 μm. (3) The composite laminate component according to (1) or (2) above, wherein the ceramic dielectric layer contains a titanium oxide dielectric. (4) The composite laminate component according to any one of (1) to (3) above, wherein the capacitor chip body and the inductor chip body are co-fired. (5) The above (1) in which one or more intermediate layers are provided between the capacitor chip body and the inductor chip body.
The composite laminate component according to any one of 1) to (4). (6) The above (wherein the intermediate layer contains a mixed material of a dielectric material substantially the same as the ceramic dielectric layer and a magnetic material substantially the same as the ceramic magnetic layer)
5) The composite laminate component described in 5). (7) The above (wherein the weight ratio of the magnetic material to the dielectric material in the mixed material of the intermediate layer is 1/9 to 9/1)
6) The composite laminate component described in 6). (8) In the above (6) or (7), the intermediate layer has two or more layers, and the weight ratio of the magnetic material to the dielectric material in the mixed material of the intermediate layer is larger toward the inductor chip body. Composite laminate parts as described. (9) The composite laminate component according to any one of (1) to (8) above, which is heat-treated in an atmosphere containing excess oxygen from the atmosphere during and/or after firing. (10) The composite laminate component according to (9) above, wherein the oxygen partial pressure ratio in the atmosphere is 30 to 100%.

0010

[Operation] The composite laminate component of the present invention has irregularities formed on the surface of the ceramic magnetic layer of the inductor chip body closest to the capacitor chip body and/or on the surface of the ceramic dielectric layer of the capacitor chip body closest to the inductor chip body. It is produced by post-firing.

[0011] By making the bonding interface between the ceramic magnetic layer and the ceramic dielectric layer uneven in this manner, local precipitation of Cu, Cu oxide, Zn, Zn oxide, etc. at the interface can be suppressed. Formation of a layer with low electrical resistance can be prevented. Therefore, a composite laminated component with sufficiently high circuit resistance can be realized.

0012

[Specific Configuration] The specific configuration of the present invention will be explained in detail below.

A laminated ceramic LC composite part, which is a preferred embodiment of the composite laminated part of the present invention, is shown in FIGS. 1 and 9.

LC composite part 1 shown in FIGS. 1 and 9
integrates a capacitor chip body 2 formed by laminating a ceramic dielectric layer 21 and an internal electrode layer 25 and an inductor chip body 3 formed by laminating a ceramic magnetic layer 31 and an internal conductor 35. It has an external electrode 51 on its surface.

As shown in FIG. 1, the present invention is characterized in that the surface of the ceramic magnetic layer 31 closest to the capacitor chip body 2 and/or the surface of the ceramic dielectric layer 21 closest to the inductor chip body 3 is provided with unevenness. After forming, firing is performed, and when the ceramic magnetic layer 31 and the ceramic dielectric layer 21 are directly bonded and integrated as shown in the example, the interface between the ceramic magnetic layer 31 and the ceramic dielectric layer 21 is Create an uneven shape. Note that in FIG. 9, the unevenness is omitted. In this case, due to mutual diffusion caused by firing, the outline of the unevenness becomes unclear to some extent, but it is possible to observe the degree of firing of the ceramic dielectric layer and ceramic magnetic layer using a scanning electron microscope (SEM), for example. , which can be distinguished from the conventional flat interface.

[0016] There are no particular restrictions on the various conditions such as the shape, pattern, and dimensions of the unevenness, and they may be appropriately selected depending on the application, but these will be detailed in the manufacturing method described later.

The material of the ceramic magnetic layer 31 of the inductor chip body 3 is Ni--Cu--Zn ferrite and/or Ni--Zn ferrite, especially Ni--Cu--Z.
n-ferrite is used.

The Ni-Zn ferrite used in the present invention is not particularly limited and may be selected from various compositions depending on the purpose. For example, the NiO content may be 10 to 25 mol%, the ZnO content may be Preferably, the amount is 15 to 40 mol%.

[0019] Further, the Ni-Cu-Zn ferrite used in the present invention is not particularly limited and may be selected from various compositions depending on the purpose. For example, the NiO content may be
15-25 mol%, CuO content is 5-15 mol%
, the content of ZnO is preferably 20 to 30 mol%.

[0020] In addition, Co, Mn, etc. contribute to the total 5w.
The content may be about t% or less. Furthermore, Ca, S
It may contain about 1 wt% or less of i, Bi, V, Pb, etc.

[0021] When Ni--Zn ferrite is used, it usually further contains various glasses such as borosilicate glass.

In the present invention, there is no particular restriction on the conductive material constituting the internal conductor 35, and Ag, Pt, Pd, Au, C
The material may be selected from u, Ni, and alloys containing one or more of these, such as Ag-Pd alloys, but in order to obtain a practical Q as an inductor, it is necessary to have a low resistivity. It is preferable to use Ag, Cu, and alloys containing one or more of these.

The inductor chip body 3 of the LC composite component 1 may have a conventionally known structure, and its outer shape is usually approximately rectangular parallelepiped. As shown in FIG. 1, the internal conductor 35 is normally arranged in a spiral shape within the magnetic layer 31 to constitute an internal winding, and both ends thereof are connected to the respective external electrodes 51, 5.
Connected to 1.

In such a case, the winding pattern of the internal conductor 35, that is, the shape of the closed magnetic circuit, can be made into various patterns, and the number of turns can be selected as appropriate depending on the application. Further, the dimensions of each part of the inductor chip body 3 are not limited, and may be appropriately selected depending on the application.

Note that the thickness of the internal conductor 35 is usually 5 to 3 mm.
The winding pitch is usually about 40 to 100 μm, and the number of turns is usually about 1.5 to 50.5 turns. Further, the base thickness of the magnetic layer 31 is usually 250 to 500 μm.
The thickness of the magnetic layer between the inner conductors 35 and 35 is usually 10~
It should be about 100 μm.

The ceramic dielectric layer 21 of the capacitor chip body 2 is not particularly limited and various dielectric materials may be used, but it is preferable to use a titanium oxide dielectric material because of its low firing temperature. In addition, titanate-based composite oxides, zirconate-based composite oxides, or mixtures thereof can also be used. Further, in order to lower the firing temperature, glass such as borosilicate glass may be included.

Specifically, as the titanium oxide type, NiO, CuO, Mn3 O4, Al2 O3,
Examples of titanic acid-based composite oxides include MgO, SiO2, etc., especially TiO2 containing CuO, and BaTiO3,
SrTiO3, CaTiO3, MgTiO3 and mixtures thereof are used as zirconate complex oxides such as Ba
ZrO3, SrZrO3, CaZrO3, MgZ
Examples include rO3 and mixtures thereof.

In the present invention, the conductive material constituting the internal electrode layer 25 is not particularly limited, and may include Ag, Pt, Pd, Au,
Cu, Ni, Ag-Pd alloy, etc.
It may be selected from alloys containing more than 100% of Ag.
, Ag alloys such as Ag-Pd alloys are suitable.

The capacitor chip body 2 of the LC composite component 1 may have a conventionally known structure, and its outer shape is usually approximately rectangular parallelepiped. As shown in FIG. 1, one end of the internal electrode layer 25 is connected to the external electrode 51.

There are no particular restrictions on the dimensions of each part of the capacitor chip body 2, and they may be selected as appropriate depending on the intended use.

The number of dielectric layers 21 to be laminated may be determined depending on the purpose, but is usually about 1 to 100. Also,
The thickness of each layer of the dielectric layer 21 is usually 20 to 150 mm.
The thickness of each layer of the internal electrode layer 25 is usually about 5 to 30 μm.

There is no particular restriction on the conductive material constituting the external electrode 51 of the LC composite component 1 of the present invention; for example, Ag, Pt
, Pd, Au, Cu, Ni, and alloys containing one or more of these, such as Ag-Pd alloys, and Ag alloys such as Ag and Ag-Pd alloys are particularly suitable. Further, the shape and dimensions of the external electrode 51 are not particularly limited and may be appropriately determined depending on the purpose and use, but the thickness is usually about 100 to 2500 μm.

The dimensions of the LC composite component 1 of the present invention are not particularly limited and may be selected appropriately depending on the purpose and use, but are usually (2.0 to 10.0 mm) x (1.2 to 15 mm). .0
mm)×(1.2 to 5.0 mm).

Next, a laminated ceramic LC composite component which is a more preferred embodiment of the composite laminate component of the present invention is shown in FIGS. 2 and 10.

The LC composite component 1 shown in FIG. 2 and FIG. The inductor chip body 3 is integrated with an inductor chip body 3 formed by laminating layers of inductor chips 3 through an intermediate layer 4, and has an external electrode 51 on the surface.

By providing one or more intermediate layers 4,
The difference in thermal expansion coefficient between the ceramic magnetic layer 31 and the ceramic dielectric layer and the steep change in composition at the interface are alleviated, and the precipitation of Cu, Cu oxide, Zn and Zn oxide at the interface is further reduced, and the parts circuit resistance is improved.

When the intermediate layer 4 is provided, the interface between the ceramic dielectric layer 21 and the intermediate layer 4 and/or the interface between the ceramic magnetic layer 31 and the intermediate layer 4 is made to have an uneven shape.

In this case, since Cu, Zn, etc. are mainly deposited at the interface between the ceramic dielectric layer 21 and the intermediate layer 4, it is preferable to deposit the deposits at the interface between the ceramic dielectric layer 21 and the intermediate layer 4, more preferably at the interface shown in FIG. As shown in FIG. 2, the interface between the ceramic dielectric layer 21 and the intermediate layer 4 and the interface between the ceramic magnetic layer 31 and the intermediate layer 4 are each made to have an uneven shape. In addition,
In FIG. 10, the unevenness is omitted.

The intermediate layer 4 is made of, for example, a magnetic material, a dielectric material, a non-magnetic Zn ferrite, etc., or glass or the like is added, and the thermal expansion coefficient of the intermediate layer 4 is equal to that of the ceramic dielectric layer 21 and the ceramic magnetic material. It is preferable to set the value to be about the middle value of the layer 31. In particular, it is preferable to include a mixed material in which a dielectric material substantially the same as that of the ceramic dielectric layer 21 and a magnetic material substantially the same as that of the ceramic magnetic layer 31 are mixed. Also,
When using the mixed material, the dielectric material and the magnetic material need only be substantially the same, but it is particularly preferable that the dielectric material and the magnetic material are the same.

Further, although the intermediate layer 4 is a single layer in the illustrated example, when the above-mentioned mixed material is used, it is preferable to have a multilayer structure of two or more layers.

[0041] The term "substantially the same materials" refers not only to cases in which the compositions are completely the same, but also cases in which the compositions are slightly different, for example, if a component containing 10 mol% or more is 30%
This includes cases in which the relative ratio is within the following range.

For example, when the magnetic material of the ceramic magnetic layer 31 is Ni-Cu-Zn ferrite, the difference in Ni content is about 3 mol % or less in terms of NiO, and the difference in Cu content is 2 mol % in terms of CuO. % or less, and if the difference in Zn content is less than about 4 mol% in terms of ZnO, they are substantially the same, and in the case of Ni-Zn ferrite, the difference in Ni content is about 5 mol% in terms of NiO. Hereinafter, if the difference in Zn content is about 5 mol % or less in terms of ZnO, they are substantially the same.

In this case, the Ni-Cu-
Zn ferrite and Ni-Zn ferrite contain Co, M
n, etc. may be contained in an amount of about 5 wt% or less of the total, and Ca, Si, Bi, V, Pb, etc. may be contained in an amount of about 1 wt% or less.

Further, in the case of Ni--Zn ferrite, various glasses such as borosilicate glass are usually added in order to lower the firing temperature.

For example, if the dielectric material of the ceramic dielectric layer 21 is a titanium oxide dielectric, the difference in Ti content is about 10 wt% or less in terms of TiO2, and if it further contains Cu, etc. The difference in content of Cu
They are substantially the same if they are each about 7 wt% or less in terms of each oxide such as O.

In this case, various glasses such as borosilicate glass may be added to lower the firing temperature.

The content ratio of the dielectric material and the magnetic material in the mixed material of the intermediate layer 4 is not particularly limited, but the content ratio of the magnetic material W2 to the content W1 of the dielectric material, that is, the weight ratio W2 /W1 is preferably 1/9 to 9/1.

In the case of the above range, Cu, Cu oxide, Zn
Local precipitation of Zn oxides and Zn oxides is further reduced.

[0049] The thickness of the intermediate layer 4 is not particularly limited and may be appropriately selected depending on the application, etc., but is usually 5 to 150 μm.
That's about it.

Further, there is no particular restriction on the number of laminated layers of the intermediate layer 4, and it may have a single layer structure as shown in the illustrated example, but Cu, Z
In order to further reduce the precipitation of n, etc., a multilayer structure with two or more layers is used, and the layer closer to the inductor chip body has a lower W2/W1.
It is preferable to use a layer of mixed material that provides a large value. In this case, W2 /W1 of each layer is, for example, 1/9 to
It may be set within the range of 9/1, and it is preferable that the total weight ratio W2 /W1 of the entire intermediate layer is about 5/5.

[0051] In the case of multiple layers, there is no particular restriction on the number of laminated layers;
The number of laminated layers is usually about 1 to 5 when considering workability etc., although it may be selected as appropriate depending on the purpose and the like. Note that the total thickness of the intermediate layer may be the same as described above, and the thickness of each layer may be different or the same.

When installing the intermediate layer 4 as described above,
Before firing, there is a certain degree of steep change in composition at the interface between the ceramic magnetic layer 31, the intermediate layer 4, and the ceramic dielectric layer 21, and each layer can be clearly distinguished.
Mutual diffusion occurs due to firing or baking of the external electrode 51, and after firing, the layer becomes a layer having a substantially continuous or gently sloped profile.

Note that the structure other than the intermediate layer 4, such as the ceramic dielectric layer 21, the internal electrode layer 25, the ceramic magnetic layer 31, the internal conductor 35, and the external electrode 51, dimensions, etc., are the same as those without the intermediate layer described above. And it is sufficient.

The composite laminate component of the present invention is not limited to the LC composite component described above, but may be any other type of composite laminate component as long as it partially has the above-described structure.

[0055] Composite laminate parts such as the LC composite part 1 of the present invention can be manufactured by a conventional printing method using paste or a sheet method.

The ceramic magnetic layer paste is prepared as follows.

First, raw material powder of ferrite, for example, Ni
Various powders such as O, ZnO, CuO, Fe2 O3, etc.
Wet mix a predetermined amount using a ball mill, etc. The particle size of the raw material powder used is approximately 0.1 to 10 μm.

[0058] The wet-mixed mixture is usually dried using a spray dryer, and then calcined. This is usually wet-pulverized using a ball mill until the particle size of the powder becomes approximately 0.01 to 0.5 μm, and then dried using a spray dryer.

The obtained ferrite powder is kneaded with a binder such as ethyl cellulose and a solvent such as terpineol or butyl carbitol to form a paste.

[0060] The paste for the magnetic layer may contain various glasses and oxides, if necessary.

There is no particular restriction on the composition of the paste for the ceramic dielectric layer, and various dielectric materials or raw material powders that become a dielectric by firing are selected depending on the composition of the ceramic dielectric layer as described above, and various binders and It can be prepared by kneading it with a solvent.

As the raw material powder, oxides constituting titanium oxide-based and titanic acid-based composite oxides may be used, and depending on the composition of the corresponding oxide dielectric, Ti, B
Oxides of a, Sr, Ca, Zr, etc. may be used.

Compounds that become oxides upon firing, such as carbonates, sulfates, nitrates, oxalates, organometallic compounds, etc., may also be used.

These raw material powders usually have an average particle size of 0.
．． A material with a diameter of about 1 to 5 μm is used.

[0065] Furthermore, various glasses may be contained as necessary.

For the paste for the intermediate layer, ferrite powder is produced in the same manner as the paste for the ceramic magnetic layer, and similarly to the paste for the ceramic dielectric layer, various dielectric materials or a dielectric material is prepared by baking depending on the desired composition. What is necessary is to select raw material powders and knead them with various binders and various solvents to adjust.

In this case, as described above, a ferrite powder having substantially the same composition, particularly the same composition, as the ferrite powder used in the paste for the ceramic magnetic layer and a raw material powder used in the paste for the ceramic dielectric layer are fired. and a raw material powder that has substantially the same composition, especially the same composition, by firing, and adjusts it to a desired mixing ratio.

Conditions such as the ferrite raw material powder, the dielectric raw material powder, and the particle size of the ferrite powder may be the same as described above.

[0069] Furthermore, various glasses and oxides may be contained as sintering aids and the like, if necessary.

Furthermore, even when a mixed material is not used, for example when non-magnetic Zn ferrite is used, a paste may be prepared in the same manner as described above.

The paste for the internal conductor, the paste for the internal electrode layer, and the paste for the external electrode are each made of the various conductive metals and alloys described above, or various oxides, organic metal compounds, and resinates that become the conductive materials described above after firing. etc., and the above-mentioned various binders and solvents are kneaded.

[0072] There is no particular restriction on the content of the binder and solvent in each of the pastes described above, and the content may be a normal content, for example,
Binder is about 1-5wt%, solvent is about 10-50wt
It may be about %. Further, each paste may contain additives selected from various dispersants, plasticizers, dielectrics, insulators, etc., as necessary. The total content of these is preferably 10 wt% or less.

In manufacturing the LC composite component 1, for example, first, a magnetic layer paste and an internal conductor paste are laminated and printed on a substrate such as PET. At this time, irregularities are formed on the surface of the magnetic layer to be printed last.

Conditions such as the shape, pattern, and dimensions of the unevenness are not particularly limited, and may be appropriately selected depending on the intended use.

For example, as the shape or pattern of the unevenness, as shown in FIGS. 3 and 4, a linear projection 61 is formed on a plane. It can also be said that the recess 65 is formed. In this case, the pattern of the concave portions 65 and convex portions 61 may be any of various striped shapes, such as the linear shape shown in the illustrated example, wavy lines, curved lines, polygonal lines, ring shapes, and closed curves and polygonal lines. It may be.

Further, as for the shape or pattern of the unevenness, as shown in FIG. Examples include those in which convex portions 61 are formed in a scattered manner, and further examples include those in which concave portions 65 and convex portions 61 are formed in contact with each other as shown in FIG. In this case, the shape of the concave portion 65 and the convex portion 61 may be any shape such as an ellipse, a polygon, etc., in addition to the circle, triangle, and quadrilateral shown in the illustrated example.

[0077]Although the illustrated example of the uneven pattern is formed regularly in terms of shape, size, arrangement, etc., it may be irregular in some cases, or may be formed by combining various types of unevenness. Good too.

Regarding the dimensions of the unevenness, it is preferable that the height h of the convex portion 61 is 3 to 30 μm. If it is less than the above range or exceeds the above range, the ability to prevent precipitation of Cu, Zn, etc. will be insufficient. Note that the height h of the convex portion 61 can be rephrased as the depth of the concave portion 65.

Further, when the convex portions 61 are provided in a striped shape, the width thereof is approximately 0.5 to 2.5 mm, and when provided in a dotted manner, the area is approximately 12 to 27 mm 2 .

The area ratio of the convex portions 61 to the concave portions 65 is preferably about 3/7 to 7/3, particularly about 1/1. Further, it is preferable that the concave portions 65 and the convex portions 61 are uniformly distributed.

After printing the paste for the magnetic layer in such an uneven shape, the paste and the paste for the internal electrode layer are laminated and printed to form a green chip. At this time, the surface of the dielectric layer printed adjacent to the magnetic layer on the magnetic layer side is formed with unevenness that corresponds to the uneven pattern of the magnetic layer, so that the bonding interface can be formed into a desired uneven shape.

Next, after cutting into a predetermined shape, it is peeled off from the substrate.

[0083] A green sheet is formed using the paste for the magnetic layer and the paste for the dielectric layer, and after printing the paste for the internal conductor and the paste for the internal electrode layer on this, these are laminated to form a green chip. may be formed. In this case, the dielectric layer adjacent to the magnetic layer may be printed directly.

Further, when forming the intermediate layer 4, the paste for the intermediate layer may be printed on the paste for the magnetic layer, and then the paste for the dielectric layer may be printed. In this case as well, the interface between the magnetic layer and the intermediate layer and the interface between the dielectric layer and the intermediate layer are made to have an uneven shape in the same manner as described above.

Next, the external electrode paste is printed or transferred onto the green chip, and the magnetic layer paste, internal conductor paste, dielectric layer paste, internal electrode layer paste, external electrode paste, and intermediate layer are formed. If so, the paste for the intermediate layer is additionally fired at the same time.

[0086] Alternatively, the chip body may be fired first, and then the paste for external electrodes may be printed and fired.

[0087] The firing temperature is 800 to 930°C, especially 85°C.
It is preferable to set it as 0-900 degreeC. Further, the firing time is preferably 0.05 to 5 hours, particularly 0.1 to 3 hours. Firing is usually performed in air.

[0088] Furthermore, the firing temperature for baking the external electrodes is usually about 500 to 700°C, and the firing time is usually about 10°C.
The firing time is approximately 30 minutes, and firing is usually performed in air.

In the present invention, it is preferable to carry out heat treatment in an atmosphere containing more oxygen than the atmosphere during and/or after firing.

By performing heat treatment in an oxygen-rich atmosphere, metals such as Cu, Zn, Cu2O, Zn2O
It is possible to precipitate or previously precipitated substances in the form of oxides with low resistance, such as CuO, ZnO, etc., in the form of oxides with high resistance and no actual damage, such as CuO and ZnO. Therefore, the circuit resistance of the component is further improved.

[0091] Furthermore, the heat treatment is preferably carried out during and/or after the final firing.

For example, when firing the chip body and firing for baking the external electrodes are performed at the same time, the firing for baking the external electrodes is performed during and/or after the firing of the chip body. In this case, it is preferable to perform a predetermined heat treatment when and/or after baking the external electrodes. Note that in the case of performing twice firing as in the latter case, heat treatment may be further performed during or after firing the chip body, depending on the case.

[0093] The oxygen partial pressure ratio in the heat treatment atmosphere is 30 to 1.
00%, more preferably 50 to 100%, particularly preferably 100%.

[0094] Below the above range, Cu, Zn, Cu2
The ability to suppress precipitation of O, Zn2O, etc. is reduced.

[0095] Such heat treatment in an oxygen-rich atmosphere is usually performed at the same time as firing and baking the external electrodes, so the various conditions such as heat treatment temperature and holding time are the same as the firing conditions and the baking conditions for the external electrodes. However, when heat treatment is performed alone, the heat treatment temperature is preferably 550 to 900°C, particularly 650 to 800°C, and the holding time is preferably 0.5 to 2 hours, particularly 1 to 1.5 hours. .

Note that composite laminated parts other than LC composite parts may also be manufactured as described above.

The composite laminated component of the present invention, such as the LC composite component manufactured in this way, can be mounted on a printed circuit board by soldering the external electrodes, etc., and used in various electronic devices. .

[0098]

[Examples] Hereinafter, the present invention will be explained in more detail by giving specific examples of the present invention.

Example 1 [Preparation of LC composite parts] The following pastes were prepared. (Magnetic layer paste) NiO (17 mol%), CuO (9 mol%), ZnO (
25 mol%) and Fe2O3 (49 mol%) powders were wet mixed using a ball mill, and then this wet mixture was dried with a spray dryer, calcined at 750°C, and made into granules. This was ground in a ball mill and then dried in a spray dryer to obtain Ni--Cu--Zn ferrite raw material powder with an average particle size of 0.1 μm. Next, for 100 parts by weight of this raw material powder,
3.84 parts by weight of ethyl cellulose and 78 parts by weight of terpineol were added and kneaded using a three-roll mill to form a paste.

(Paste for internal conductor) Average particle size 0.8μ
2.m of ethyl cellulose per 100 parts by weight of Ag.
5 parts by weight and 40 parts by weight of terpineol were added and kneaded using three rolls to form a paste.

(Paste for dielectric layer) Average particle size 0.7μ
m TiO2 (92 mol%), average particle size 0.05 μm
of CuO (4 mol%) and Ni with an average particle size of 0.5 μm
O (4 mol%) was used. To 100 parts by weight of this dielectric powder, 3.5 parts by weight of ethyl cellulose and 40 parts by weight of terpineol were added and kneaded using three rolls to form a paste.

(Paste for internal electrode layer) Average particle size 0.8
For every 100 parts by weight of μm Ag, 2.
5 parts by weight and 40 parts by weight of terpineol were added and kneaded using a three-roll mill to form a paste.

(Paste for intermediate layer) ZnO (50 mol %) with a particle size of about 0.8 μm and Fe2 O3 (50 mol %)
A raw material powder of non-magnetic Zn ferrite having an average particle size of 0.2 μm was prepared in the same manner as the paste for the magnetic layer. Next, for 100 parts by weight of this raw material powder,
3.5 parts by weight of ethyl cellulose and 40 parts by weight of terpineol were added and kneaded using a triple roller to form a paste.

(Paste for external electrode) Average particle size 1.2μ
3.0 parts by weight of ethyl cellulose per 100 parts by weight of Ag
Parts by weight, 7 parts by weight of glass frit, 40 parts by weight of terpineol
Parts by weight were added and kneaded using three rolls to form a paste.

The paste for the magnetic layer and the paste for the internal conductor produced in this manner are printed and laminated, then the paste for the intermediate layer is printed, and then the paste for the dielectric layer and the paste for the internal electrode layer are printed. They were laminated to form a green chip.

In this case, on the surface of the intermediate layer on the dielectric layer side,
Striped convex portions 61 as shown in FIG. 3 were regularly formed to give an uneven shape to the interface between the intermediate layer and the dielectric layer. The height h of the convex portions 61 was 10 μm, the width was 1 mm, and the pitch was 2 mm. Further, the thickness of the intermediate layer was 50 μm.

[0107] Next, it was fired in air at 890°C for 2 hours.

After baking, a paste for external electrodes was printed, and then baked in air at 600° C. for 30 minutes to bake the external electrodes.

[0109] In this way, 5.0 mm x 5.0 mm x
LC filter composite part sample No. 2.7 mm shown in FIG. 1 was produced.

The thickness of the magnetic layer was 40 μm, the thickness of the internal winding (internal conductor) was 15 μm, and the wire width was 300 μm. The number of turns was 25 turns.

The thickness of the dielectric layer was 100 μm, the number of laminated dielectric layers was 5, and the thickness of the internal electrode layer was 15 μm. The thickness of the external electrode was 800 μm.

[0112] Sample No. 1 was also used, except that the interface between the intermediate layer and the dielectric layer was not made uneven. Comparative sample No. 1 was prepared in the same manner as No. 1. 2 was produced.

[0113] Also, except that the firing temperature was 870°C and 850°C, No. Sample No. 1 was prepared in the same manner as in Sample No. 1. 3(
(fired at 870°C), No. 5 (fired at 850°C), and No. 5, except that the firing temperature was 870°C and 850°C.
．． Sample No. 2 was prepared in the same manner as in Sample No. 2. 4 (fired at 870°C), No. 6 (fired at 850°C) were prepared.

[0114] Each sample obtained was subjected to X-ray analysis to determine the concentration distribution of Zn and Cu in the vicinity of the joint between the capacitor chip body and the inductor chip body.

As a result, sample No. of the present invention. 1,
No. 3 and no. 5, Cu, Cu,
There was almost no precipitation of Zn or the like. On the other hand, comparative sample No. 2 is C at the interface between the dielectric layer and the intermediate layer.
Precipitation of u, Zn, etc. was confirmed.

Next, the circuit resistance IR of each sample was measured. The results are shown in Table 1.

[0117]

[Table 1]

The effects of the present invention are clear from the results shown in Table 1.

[0119] In addition, similar results were obtained when various samples were prepared with different unevenness patterns at the interface between the dielectric layer and the intermediate layer.

[0120] Also, instead of the interface between the dielectric layer and the intermediate layer,
Furthermore, when various samples were prepared in which the interface between the dielectric layer and the intermediate layer as well as the interface between the magnetic layer and the intermediate layer had an uneven shape, the circuit resistance IR was the highest in the sample with uneven surfaces on both interfaces. The sample with the interface unevenness between the body layer and the intermediate layer had the second highest value, the sample with the interface unevenness between the magnetic layer and the intermediate layer had the third highest value, and the sample with no unevenness had the lowest.

[0121] Also, Ni-Cu-Zn ferrite is
- Create a paste by adding glass frit instead of Zn ferrite, and replace TiO2 and CuO with TiO2
When pastes were prepared by adding glass frit instead of the wafer, and various samples were prepared using these pastes, similar results were obtained.

[0122] In addition to LC filter composite parts, LC
Similar results were obtained when composite laminated parts such as traps were made.

Example 2 Samples shown in FIG. 9 similar to Example 1 except that no intermediate layer was formed were prepared, and a decrease in circuit resistance IR was confirmed compared to the sample of Example 1. It was done. Note that in this case, the interface between the magnetic layer and the dielectric layer has an uneven shape.

Example 3 A paste for an intermediate layer containing the following mixed material was prepared.

(Paste for intermediate layer containing mixed materials) 100 parts by weight of the Ni-Cu-Zn ferrite raw material powder used in the paste for the magnetic layer in Example 1 and 100 parts by weight of the dielectric powder used in the paste for the dielectric layer. 3.5 parts by weight of ethyl cellulose and 40 parts by weight of terpineol were added and kneaded using a three-roll mill to form a paste.

[0126] When samples were prepared in the same manner as in Example 1 except that the intermediate layer was formed using the intermediate layer paste containing the mixed material, it was confirmed that the circuit resistance IR was improved compared to the sample of Example 1. It was done.

Example 4 Samples were prepared in the same manner as in Example 3 except that the single intermediate layer was changed to three layers. In this case, among the three intermediate layers, the intermediate layer on the magnetic layer side has a dielectric powder content of W1.
, when the content of the Ni-Cu-Zn raw material powder is W2, the weight ratio W2 /W1 is 7/3, the central intermediate layer has a W2 /W1 ratio of 5/5, and the intermediate layer on the dielectric layer side has a weight ratio of 7/3. teeth,
A paste blended so that W2/W1 was 3/7 was used. Further, the thickness of each of the three layers was 20 μm, and the total thickness of the intermediate layer was 60 μm.

As a result, it was confirmed that the circuit resistance IR was improved compared to the sample of Example 3.

Example 5 In Examples 1 to 4, the baking in air was replaced with baking that also served as heat treatment in an oxygen atmosphere with an oxygen partial pressure ratio of 100%, and the baking of the external electrode in air was performed with an oxygen content of 100%. Pressure ratio 100%
Samples were prepared in the same manner, except that the sintering was performed in an oxygen atmosphere.

As a result, it was confirmed that the circuit resistance IR was improved compared to the sample fired in air.

[0131] Furthermore, when the precipitates at the interface between the inductor chip body and the capacitor chip body of each sample were measured by accounted for the majority. In contrast, the precipitates of the samples of Examples 1 to 4 that were not heat-treated in an oxygen-rich atmosphere were Cu, Cu2
O, Zn, and Zn2O accounted for the majority.

As described above, the effects of the present invention are clear from Examples 1 to 5.

[0133]

Effects of the Invention The composite laminate component of the present invention has a structure in which localized Cu is removed at the interface between the inductor chip body and the capacitor chip body.
There is almost no precipitation of Zn, Cu oxide, Zn or Zn oxide. Therefore, the circuit resistance of the components is high.

[Brief explanation of the drawing]

FIG. 1: LC, which is a preferred embodiment of the composite laminate component of the present invention.
FIG. 3 is a cross-sectional view showing a composite part.

FIG. 2: LC, which is a preferred embodiment of the composite laminate component of the present invention.
FIG. 3 is a cross-sectional view showing a composite part.

FIG. 3 is a partial perspective view showing one example of the magnetic layer of the composite laminate component of the present invention.

FIG. 4 is a partial perspective view showing one example of the magnetic layer of the composite laminate component of the present invention.

FIG. 5 is a partial perspective view showing an example of the magnetic layer of the composite laminate component of the present invention.

FIG. 6 is a partial perspective view showing one example of the magnetic layer of the composite laminate component of the present invention.

FIG. 7 is a partial perspective view showing an example of the magnetic layer of the composite laminate component of the present invention.

FIG. 8 is a partial perspective view showing one example of the magnetic layer of the composite laminate component of the present invention.

FIG. 9: LC, which is a preferred embodiment of the composite laminate component of the present invention.
FIG. 2 is a perspective view showing a part of the composite component cut away.

FIG. 10 is a preferred embodiment of the composite laminate component of the present invention.
It is a perspective view which shows a part of C composite part notched.

[Explanation of symbols]

1 LC composite parts 2 Capacitor chip body 21 Ceramic dielectric layer 25 Internal electrode layer 3 Inductor chip body 31 Ceramic magnetic layer 35 Internal conductor 4 Middle class 51 External electrode 61 Convex part 65 Recess

Claims (10)

[Claims] 1. A composite body integrally comprising a capacitor chip body formed by laminating a ceramic dielectric layer and an internal electrode layer, and an inductor chip body formed by laminating a ceramic magnetic layer and an internal conductor. A multilayer component, wherein the ceramic magnetic layer contains Ni-Cu-Zn ferrite and/or Ni-Zn ferrite, and the surface of the ceramic magnetic layer closest to the capacitor chip body and/or the ceramic dielectric layer A composite laminate component characterized in that it is fired after forming irregularities on the surface closest to the inductor chip body. [Claim 2] The height of the convex portion of the unevenness is 3 to 30 μm.
The composite laminate component according to claim 1. 3. The composite laminate component according to claim 1, wherein the ceramic dielectric layer contains a titanium oxide dielectric. 4. The composite laminate component according to claim 1, wherein the capacitor chip body and the inductor chip body are co-fired. 5. The composite laminate component according to claim 1, wherein one or more intermediate layers are provided between the capacitor chip body and the inductor chip body. 6. The intermediate layer includes a mixed material of a dielectric material substantially the same as the ceramic dielectric layer and a magnetic material substantially the same as the ceramic magnetic layer. Composite laminate parts as described. 7. The composite laminate component according to claim 6, wherein the weight ratio of the magnetic material to the dielectric material in the mixed material of the intermediate layer is 1/9 to 9/1. 8. The inductor according to claim 6, wherein the intermediate layer has two or more layers, and the weight ratio of the magnetic material to the dielectric material in the mixed material of the intermediate layer is larger toward the inductor chip body. composite laminate parts. 9. The composite laminate component according to claim 1, wherein the composite laminate component is heat-treated in an atmosphere containing oxygen in excess of the atmosphere during and/or after firing. 10. Oxygen partial pressure ratio in the atmosphere is 30 to 30.
The composite laminate component according to claim 9, which is 100%.