JP2021153105A - Laminate electronic part - Google Patents

Abstract

To provide a laminate electronic part which is superior in the mutual adhesion of dielectric layers while a plurality of dielectric layers are laminated therein, which is arranged so that the decrease of the specific dielectric constant of the dielectric layer can be suppressed, and which achieves good Q value.SOLUTION: A laminate electronic part comprises: a first dielectric layer having a first main component containing barium oxide, neodymium oxide, and titanium oxide; and a second dielectric layer having a second main component containing forsterite. A content C1 of zinc oxide to 100 mass% of the first main component in the first dielectric layer is 5.0 mass% or less in terms of ZnO. A content C2 of zinc oxide to 100 mass% of the second main component in the second dielectric layer is smaller than C1. A content of manganese oxide to 100 mass% of the first main component in the first dielectric layer is 2.0 mass% or less in terms of MnO. A content of manganese oxide to 100 mass% of the second main component in the second dielectric layer is 2.0 mass% or less in terms of MnO.SELECTED DRAWING: Figure 2

Description

The present invention relates to laminated electronic components.

In recent years, in the fields of mobile communication devices such as mobile phones, AV devices, computer devices, etc., with the progress of miniaturization and high performance of products, various electronic components used for these have also been miniaturized and improved in performance. Is required. Surface Mount Device (SMD) equipped with conductors such as electrodes and wiring (hereinafter referred to as "internal conductors") on the substrate in order to support such miniaturization and high performance of various electronic components. Has become the mainstream as an electronic device.

The SMD has a printed circuit board on which each component such as an IC chip and other chip components constituting an electronic device is mounted. As an electronic device mounted on an SMD, a laminated electronic component obtained by simultaneously firing a plurality of types of compositions having different material properties is used. Examples of the laminated electronic component include an LC filter made of a combination of a magnetic material and a dielectric material, a circuit board (element) having a built-in capacitor made of a combination of a high dielectric constant material and a low dielectric constant material, and the like. ..

In the case of an LC filter, select a low dielectric constant material having a high Q value so that the self-resonant frequency can be taken high for the material of the part constituting the inductance part, and select a material with good temperature characteristics and a high dielectric constant for the capacitor part. As a result, it is possible to realize an LC element having a high Q value and good temperature characteristics. Further, in the case of a capacitor, by combining a high dielectric constant material and a low dielectric constant material, the distributed capacitance can be reduced as compared with a capacitor made of only a high dielectric constant material, and compared with a capacitor made of only a low dielectric constant material. Can be miniaturized.

For example, Patent Document 1 describes a _{first dielectric layer containing BaO, Nd 2} O ₃ and TiO ₂ , a second dielectric layer containing forsterite and the like, and a first dielectric layer and a second dielectric layer. A ceramic electronic component having a boundary reaction layer containing ZnO or the like formed between them is disclosed.

Patent Document 2 discloses a composite laminated ceramic electronic component including a low dielectric constant ceramic layer and a high dielectric constant ceramic layer. Further, Patent Document 2 discloses that the low dielectric constant ceramic layer and the high dielectric constant ceramic layer have the same constituent components, but good dielectric properties can be obtained by different content ratios thereof. There is.

Japanese Patent No. 5152308 Japanese Patent No. 5435176

However, the ceramic electronic component described in Patent Document 1 has a problem that the relative permittivity of the dielectric layer is lowered due to the boundary reaction layer.

Further, the composite laminated ceramic electronic component described in Patent Document 2 has a problem that the Q value is low.

The present invention has been made in view of such an actual situation, and even if a plurality of dielectric layers are laminated, the adhesion between the dielectric layers is excellent, the decrease in the relative permittivity of the dielectric layers is suppressed, and the Q value is suppressed. It is an object of the present invention to provide a good laminated electronic component.

In order to achieve the above object, the laminated electronic component of the present invention is used.
[1] A first dielectric layer having a first principal component containing barium oxide, neodymium oxide, and titanium oxide,
An electronic component comprising a second dielectric layer having a second principal component containing forsterite.
In the first dielectric layer, when the content ratio of zinc oxide to 100% by mass of the first principal component is C1, C1 is 5.0% by mass or less in terms of ZnO.
In the second dielectric layer, when the content ratio of zinc oxide with respect to 100% by mass of the second main component is C2, C2 is smaller than C1.
In the first dielectric layer, the content ratio of manganese oxide to 100% by mass of the first main component is 2.0% by mass or less in terms of MnO, and in the second dielectric layer, manganese oxide to 100% by mass of the second main component. It is a laminated electronic component having a content ratio of 2.0% by mass or less in terms of MnO.

[2] C2 is the laminated electronic component according to [1], which is 2.0% by mass or less.

[3] The first principal component is the laminated electronic component according to [1] or [2], which further has forsterite.

[4] The laminated electronic component according to any one of [1] to [3], further comprising lithium-containing glass, the first dielectric layer and the second dielectric layer.

[5] The second dielectric layer further contains an alkaline earth metal oxide, boron oxide and copper oxide, and the content ratio of the alkaline earth metal oxide to 100% by mass of the second main component is 0.2 in RO conversion. Mass% or more and 4.0 mass% or less,
The content of boron oxide to the second principal component 100 weight% is at _B 2 _{O 3} 3.0 wt% to 0.2 wt% in terms of the following,
The laminated electronic component according to any one of [1] to [4], wherein the content ratio of copper oxide with respect to 100% by mass of the second main component is 0.5% by mass or more and 3.0% by mass or less in terms of CuO.

[6] The softening point of the lithium-containing glass contained in the first dielectric layer is 570 ° C. or lower, and the crystallization point of the lithium-containing glass contained in the second dielectric layer is 500 ° C. or lower.
In the first dielectric layer, when the first dielectric layer does not contain silver, the content ratio of the lithium-containing glass to the total 100% by mass of the first main component, the first main component, and the components excluding the lithium-containing glass is 2. It is 0.0% by mass or more and 10.0% by mass or less,
In the first dielectric layer, when the first dielectric layer contains silver, the content ratio of the lithium-containing glass to the total 100% by mass of the first main component, the first main component, the lithium-containing glass and the components excluding silver is 2.0% by mass or more and 10.0% by mass or less,
In the second dielectric layer, the content ratio of the lithium-containing glass to 100% by mass of the total of the second main component, the second main component and the components excluding the lithium-containing glass is 2.0% by mass or more and 10.0% by mass or less. The laminated electronic component according to any one of [3] to [5].

[7] The second dielectric layer further contains titanium oxide, and the content ratio of titanium oxide to 100% by mass of the second main component is 0.3% by mass or more and 3.0% by mass or less in terms of _{TiO 2 [1].} ] To [6].

[8] The second dielectric layer further contains aluminum oxide, and the content ratio of aluminum oxide with respect to 100% by mass of the second main component is 0.3% by mass or more and 3.0% by mass or less in terms of _{Al 2} O _3. The laminated electronic component according to any one of [1] to [7].

[9] Barium oxide, neodymium oxide, titanium oxide contained in the first principal component, and forsterite are represented by the composition formula {α (BaO · Nd ₂ O ₃ · TiO ₂ ) + β ( ₂ MgO · SiO 2)}. When you do
Described in any one of [3] to [8], wherein α and β indicate a volume ratio and satisfy the relationships of 35% by volume ≤ α ≤ 65% by volume, 35% by volume ≤ β ≤ 65% by volume, and α + β = 100. It is a laminated electronic component.

According to the present invention, even if a plurality of dielectric layers are laminated, the adhesiveness between the dielectric layers is excellent, the decrease in the dielectric constant of the dielectric layers is suppressed, and a laminated electronic component having a good Q value is provided. can do.

FIG. 1 is a schematic cross-sectional view of an LC filter according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view of the composite chip produced in the examples.

Hereinafter, the present invention will be described in detail in the following order based on specific embodiments.
1. 1. Laminated electronic components 1.1 Overall configuration of LC filter 1.2 First dielectric layer 1.3. Second dielectric layer 2. Manufacturing method of laminated electronic components 3. Modification example

(1. Laminated electronic components)
An LC filter, which is a composite electronic component, will be described as an example of the laminated electronic component according to the present embodiment.

(1.1 Overall configuration of LC filter)
FIG. 1 is a schematic cross-sectional view of an LC filter. The LC filter 1 has a capacitor portion 10 and an inductance portion 20. In the present embodiment, as shown in FIG. 1, the inductance portions 20 are arranged above and below the capacitor portion 10, and the LC filter 1 has a configuration in which the capacitor portion 10 is sandwiched between the inductance portions 20.

The capacitor portion 10 has a structure in which a plurality of dielectric layers 11 and a plurality of internal electrode layers 12 are alternately laminated, and the dielectric layer 11 is composed of a first dielectric layer described later. On the other hand, the inductance portion 20 has a structure in which a coil conductor 22 having a predetermined pattern is formed in the dielectric layer 21, and the dielectric layer is composed of a second dielectric layer described later.

The internal electrode layer in the capacitor portion 10 and the coil conductor in the inductance portion 20 are drawn out to the surface of the LC filter 1 in a cross section different from the cross section shown in FIG. 1, and the external electrodes formed on the surface of the LC filter 1 ( It is electrically connected to (not shown). Further, the internal electrode layer 12 and the coil conductor 22 are electrically connected to each other.

The conductive material contained in the internal electrode layer 12 constituting the capacitor portion 10 or the coil conductor 22 constituting the inductance portion 20 is not particularly limited, but the first dielectric layer and the second dielectric layer described later are at low temperatures. Since it can be produced by firing, in this embodiment, it is preferable to use silver having a low DC resistance or a silver alloy containing silver as a main component as the conductive material.

The conductive material contained in the external electrode is not particularly limited, but a conductive material containing silver can be used. Further, the external electrode is preferably plated with a known metal or alloy.

The shape of the LC filter 1 is not particularly limited, but is usually a rectangular parallelepiped shape. Further, the dimensions are not particularly limited, and the dimensions may be appropriate according to the intended use.

(1.2 First Dielectric Layer)
In the present embodiment, the first dielectric layer is a dielectric layer constituting the capacitor portion 10. The first dielectric layer has a first principal component. The content ratio of the first principal component in the first dielectric layer is preferably 70% by mass or more, and more preferably 80% by mass or more, when the entire first dielectric layer is 100% by mass.

The first principal component contains at least a composite oxide containing barium oxide (BaO), neodymium oxide (Nd ₂ O ₃ ) and titanium oxide (TiO _2). Specifically, the first principal component preferably contains a composite oxide such as _{BaO-Nd 2} O _{3 -TIO 2} system and Bi ₂ O _3- BaO-Nd ₂ O _3- TiO _{2 system.}

When the BaO-Nd ₂ O _3- TiO _2- based composite oxide is represented by the composition formula xBaO · yNd ₂ O ₃ · zTiO ₂ , x, y and z indicating the molar ratio of each oxide are 14.0 ≦ x. It is preferable to satisfy the relationship of ≦ 19.0, 12.0 ≦ y ≦ 17.0, 65.0 ≦ z ≦ 71.0, and x + y + z = 100.

In this embodiment, the first principal component, in addition to _BaO-Nd 2 O 3 -TiO ₂ composite oxide preferably contains forsterite _{(2MgO-SiO 2, Mg 2} SiO 4).

_{The BaO-Nd 2} O _3- TiO _2- based composite oxide contained in the first principal component and forsterite have a composition formula {α (BaO · Nd ₂ O ₃ · TiO ₂ ) + β ( ₂ MgO · SiO 2)}. Can be represented by. In the composition formula, α indicates _{the volume ratio (%) of the BaO-Nd 2} O _3- TiO _2- based composite oxide, β indicates the volume ratio (%) of forsterite, and α + β = 100.

In the present embodiment, α and β preferably satisfy the relationship of 35% by volume ≤ α ≤ 65% by volume and 35% by volume ≤ β ≤ 65% by volume, and 45% by volume ≤ α ≤ 65% by volume and 35. It is more preferable to satisfy the relationship of volume% ≤ β ≤ 55 volume%.

The BaO-Nd ₂ O _3- TiO _2- based composite oxide has a relatively high relative permittivity εr, and the value of the relative permittivity εr is about 55 to 105. On the other hand, forsterite has a relatively low relative permittivity εr, and the value of the relative permittivity εr is about 6.8. Therefore, in the first main component, _{the content ratio of the BaO-Nd 2} O _3- TiO _2- based composite oxide having a high relative permittivity εr and the content ratio of forsterite having a low relative permittivity εr are within the above ranges. By changing it, the relative permittivity of the first dielectric layer can be adjusted.

The Q / f value of the BaO-Nd ₂ O _3- TiO _2- based composite oxide is about 2000 to 8000 GHz. On the other hand, the Q / f value of forsterite alone is about 200,000 GHz, and the dielectric loss of forsterite is smaller than the dielectric loss of _{BaO-Nd 2} O _3- TIO _{2 compounds.}

Therefore, the dielectric loss of the first dielectric layer can be reduced by containing forsterite, which has a small dielectric loss, in addition to _{the BaO-Nd 2} O _3- TiO _2- based composite oxide as the first principal component. can.

The Q value represents the magnitude of dielectric loss, and is the reciprocal of the tangent tan δ of the loss angle δ, which is the difference between the phase difference between the actual current and voltage and the phase difference of 90 degrees between the ideal current and voltage (Q =). 1 / tan δ). The Q / f value is the product of the Q value and the resonance frequency f.

Normally, when alternating current is applied to an ideal dielectric, the current and voltage have a phase difference of 90 degrees. However, when the frequency of alternating current becomes high and the frequency becomes high, the electric polarization of the dielectric or the orientation of polar molecules cannot follow the change of the electric field at high frequency, or the electric flux density becomes higher than that of the electric field due to the conduction of electrons or ions. Therefore, there is a phase delay (phase difference), and the actual current and voltage have a phase other than 90 degrees. A phenomenon in which a part of high-frequency energy is dissipated as heat due to such a phase difference is called a dielectric loss. The smaller the dielectric loss, the larger the Q value, and the larger the dielectric loss, the smaller the Q value. Dielectric loss means the power loss of a high-frequency device, and since a high-frequency device is required to have a small dielectric loss in order to realize high characteristics, a dielectric having a large Q value is required.

The first dielectric layer may have a first subcomponent in addition to the above first principal component. As the first subcomponent, for example, zinc oxide (ZnO), manganese oxide (MnO), boron oxide (B ₂ O ₃ ), bismuth oxide (Bi ₂ O ₃ ), cobalt oxide (CoO), lithium (Li) are contained. Examples include glass and silver (Ag).

In the present embodiment, the first sub-component contained in the first dielectric layer is divided into a first sub-component A and a first sub-component B. The first subcomponent A contains zinc oxide, manganese oxide, boron oxide, bismuth oxide, and cobalt oxide, and the first subcomponent B contains lithium-containing glass and silver.

By containing zinc oxide with respect to the first subcomponent A, it becomes easy to improve the low temperature sinterability of the first dielectric layer. Assuming that the content ratio of zinc oxide with respect to 100% by mass of the first principal component is C1, C1 is 5.0% by mass or less in terms of ZnO. If the zinc oxide content (C1) is too large, the Q value of the first dielectric layer tends to decrease. The zinc oxide content (C1) is preferably 4.5% by mass or less in terms of ZnO, and more preferably 4.0% by mass or less. On the other hand, from the viewpoint of low-temperature sinterability, the zinc oxide content (C1) with respect to 100% by mass of the first principal component is preferably 1.0% by mass or more in terms of ZnO.

By containing manganese oxide, it becomes easy to improve the low temperature sinterability of the first dielectric layer. The content ratio of manganese oxide with respect to 100% by mass of the first principal component is 2.0% by mass or less in terms of MnO. If the content of manganese oxide is too large, the Q value of the first dielectric layer tends to decrease. The content ratio of manganese oxide is preferably 1.0% by mass or less, more preferably 0.5% by mass or less in terms of MnO. On the other hand, from the viewpoint of low-temperature sinterability, the content ratio of manganese oxide with respect to 100% by mass of the first principal component is preferably 0.1% by mass or more in terms of MnO.

By containing boron oxide, it becomes easy to improve the low temperature sinterability of the first dielectric layer. The content of boron oxide to the first principal component 100 _weight%, it is preferable terms _of B 2 _{O 3} at more than 0.5 mass% to 6.0 mass%. If the content of boron oxide is too small, the low temperature sinterability tends to decrease. On the other hand, if the content ratio of boron oxide is too large, the Q value tends to decrease.

By containing bismuth oxide, it becomes easy to improve the low temperature sinterability of the first dielectric layer. The content ratio of bismuth oxide to 100% by mass of the first principal component is preferably 6.0% by mass or less in terms of _{Bi 2} O _3. If the content of bismuth oxide is too small, the low temperature sinterability tends to decrease. On the other hand, if the content ratio of bismuth oxide is too large, the Q value tends to decrease.

By containing cobalt oxide, it becomes easy to improve the low temperature sinterability of the first dielectric layer. The content ratio of cobalt oxide to 100% by mass of the first principal component is preferably 6.0% by mass or less in terms of CoO. If the content of cobalt oxide is too small, the low temperature sinterability tends to decrease. On the other hand, if the content of boron oxide is too large, the low temperature sinterability tends to decrease.

With respect to the first subcomponent B, the inclusion of lithium-containing glass facilitates suppression of silver segregation, improvement of low-temperature sinterability, and improvement of electrical characteristics. The lithium-containing glass is preferably glass having a softening point of 570 ° C. or lower. In addition to the above range of softening points, it is more preferable that the glass transition point of the lithium-containing glass is 490 ° C. or lower and / or the crystallization point is 790 ° C. or lower. The softening point, glass transition point and crystallization point can be measured by a differential thermal analysis (DTA) method.

As long as the lithium-containing glass has the above physical characteristics, its composition is not particularly limited, and a known lithium-containing glass can be used. Examples of the components constituting the lithium-containing glass include a modified oxide component, a network-forming oxide component, and a metal oxide. Lithium oxide (Li ₂ O) is a modified oxide component, and the modified oxide component other than lithium oxide is at least one selected from alkaline earth oxides (RO), specifically CaO, SrO and BaO. Is exemplified. Examples of the network-forming oxide component include B ₂ O ₃ and SiO ₂ . In addition to the above-mentioned modified oxide component, any metal oxide can be used as the other modified oxide component. Specifically, Na ₂ O, K ₂ O, ZrO ₂ , Al ₂ O ₃ , ZnO, CuO, NiO, CoO, MnO, Cr ₂ O ₃ , V ₂ O ₅ , MgO, Nb ₂ O ₅ and Ta ₂ at least one selected from O ₅ is exemplified.

The content ratio of the lithium-containing glass is preferably 2.0% by mass or more and 10.0% by mass or less with respect to a total of 100% by mass of the first principal component and the first subcomponent A. If the content ratio of the lithium-containing glass is too small, the effect of suppressing silver segregation tends to decrease. On the other hand, if the content ratio of the lithium-containing glass is too large, the sheet-forming paint of the first dielectric layer tends to gel.

The content ratio of the lithium-containing glass is more preferably 3.0% by mass or more, and further preferably 4.0% by mass or more. On the other hand, the content ratio of the lithium-containing glass is more preferably 8.0% by mass or less, and further preferably 7.0% by mass or less.

The silver content is preferably 0.5% by mass or more and 2.0% by mass or less with respect to a total of 100% by mass of the first principal component and the first subcomponent A. If the silver content is too small, the low-temperature sinterability tends to decrease, and the diffusion of silver into the first dielectric layer tends to be unable to be suppressed. On the other hand, if the silver content is too large, the Q value tends to decrease, and silver tends to segregate in the first dielectric layer.

(1.3. Second dielectric layer)
In the present embodiment, the second dielectric layer is a dielectric layer constituting the inductance portion 20. The second dielectric layer is made of a material different from that of the first dielectric layer. The second dielectric layer has a second main component. The content ratio of the second principal component in the second dielectric layer is preferably 80% by mass or more, and more preferably 85% by mass or more, when the entire second dielectric layer is 100% by mass.

In the present embodiment, the relative permittivity εr of the second dielectric layer is preferably lower than the relative permittivity εr of the first dielectric layer. By doing so, it is possible to reduce unnecessary signals of the filter as compared with the case where the filter is formed only by the first dielectric layer.

Accordingly, the second principal component, the first dielectric layer to the _BaO-Nd 2 O 3 -TiO ₂ based dielectric constant εr is smaller than the composite oxide contained, and a high Q value forsterite (2MgO-SiO ₂ , Mg ₂ SiO ₄ ) is contained at least. In the present embodiment, from the viewpoint of lowering the relative permittivity εr of the second dielectric layer and increasing the Q value, it is preferable that the proportion of forsterite in the second main component is high. Specifically, the content ratio of forsterite in 100% by mass of the second main component is preferably 95% by mass or more. Examples of components other than forsterite contained in the second main component include magnesium titanate (MgTiO ₃ ) and calcium titanate (CaTIO ₃ ).

In addition to the above-mentioned second main component, the second dielectric layer contains an alkaline earth metal oxide, copper oxide (CuO), boron oxide (B ₂ O ₃ ), and lithium-containing glass as a second subcomponent. Is preferable.

In the present embodiment, the sub-component contained in the second dielectric layer is divided into a second sub-component A and a second sub-component B. The second subcomponent A contains an alkaline earth metal oxide, copper oxide and boron oxide, and the second subcomponent B contains lithium-containing glass.

By containing the alkaline earth metal oxide with respect to the second subcomponent A, it becomes easy to improve the low temperature sinterability of the second dielectric layer. The content ratio of the alkaline earth metal oxide to 100% by mass of the second main component is preferably 0.2% by mass or more and 4.0% by mass or less in terms of RO, and 0.2% by mass or more and 3.5% by mass or less. More preferably, it is less than%. Here, R is an alkaline earth metal. If the content of the alkaline earth metal oxide is too small, the low temperature sinterability will decrease. On the other hand, if the content ratio of the alkaline earth metal oxide is too large, the Q value tends to decrease.

As the alkaline earth metal, at least one selected from the group consisting of calcium (Ca), barium (Ba) and strontium (Sr) is preferable, and calcium is more preferable.

When calcium oxide (CaO) is used as the alkaline earth metal oxide, the content ratio of calcium oxide with respect to 100% by mass of the second main component is preferably 0.2% by mass or more and 3.0% by mass or less. When barium oxide (BaO) is used as the alkaline earth metal oxide, the content ratio of barium oxide to 100% by mass of the second main component is preferably 0.2% by mass or more and 3.0% by mass or less. When strontium oxide (SrO) is used as the alkaline earth metal oxide, the content ratio of strontium oxide to 100% by mass of the second main component is preferably 0.2% by mass or more and 3.0% by mass or less.

By containing copper oxide, it becomes easy to improve the low temperature sinterability and Q value of the second dielectric layer. The content ratio of copper oxide with respect to 100% by mass of the second main component is preferably 0.5% by mass or more and 3.0% by mass or less, and 0.5% by mass or more and 2.5% by mass or less in terms of CuO. Is more preferable. If the content of copper oxide is too small, the low temperature sinterability is lowered. On the other hand, if the content ratio of copper oxide is too large, the Q value tends to decrease. Further, when silver is used as the internal electrode, the silver diffuses into the second dielectric layer during firing. As a result, a gap is generated between the dielectric and the electrode, the adhesion is lowered, and the moisture resistance is lowered.

By containing boron oxide, it becomes easy to improve the low temperature sinterability of the second dielectric layer. The content of boron oxide to the second principal component 100 weight _percent, preferably B 2 _{O 3} is 0.2 wt% to 3.0 wt% or less in terms of 0.2 wt% to 2.5 wt% The following is more preferable. If the content of boron oxide is too small, the low temperature sinterability will decrease. On the other hand, if the content ratio of boron oxide is too large, the Q value tends to decrease. Further, when silver is used as the internal electrode, the silver diffuses into the second dielectric layer during firing. As a result, a gap is generated between the dielectric and the electrode, the adhesion is lowered, and the moisture resistance is lowered.

With respect to the second subcomponent B, by including the lithium-containing glass, it becomes easy to improve the low temperature sinterability and the Q value of the second dielectric layer. The lithium-containing glass is preferably a glass having a glass transition point of 430 ° C. or lower. In addition to the above range of the glass transition point, it is more preferable that the crystallization point of the lithium-containing glass is 500 ° C. or lower. The glass transition point and the crystallization point can be measured by a differential thermal analysis (DTA) method.

As long as the lithium-containing glass has the above physical characteristics, its composition is not particularly limited, and a known lithium-containing glass can be used. Examples of the components constituting the lithium-containing glass include a modified oxide component, a network-forming oxide component, and a metal oxide. Lithium oxide (Li ₂ O) is a modified oxide component, and the modified oxide component other than lithium oxide is at least one selected from alkaline earth oxides (RO), specifically CaO, SrO and BaO. Is exemplified. Examples of the network-forming oxide component include B ₂ O ₃ and SiO ₂ . In addition to the above-mentioned modified oxide component, any metal oxide can be used as the other modified oxide component. Specifically, Na ₂ O, K ₂ O, ZrO ₂ , Al ₂ O ₃ , ZnO, CuO, NiO, CoO, MnO, Cr ₂ O ₃ , V ₂ O ₅ , MgO, Nb ₂ O ₅ and Ta ₂ At least one selected from _{O 5} is exemplified, and it is preferable to use _{Al 2} O _3.

In the present embodiment, the lithium-containing _glass, SiO ₂ -RO-Li 2 O-based _{glass, B 2 O 3 -RO-Li} 2 O -based _{glass, SiO 2 -RO-Al 2 O} 3 -Li 2 O system glass And B ₂ O _3- RO-Al ₂ O _3- Li ₂ O-based glass is preferably at least one selected. Among them, lithium-containing _{glass, SiO 2 -RO-Al 2 O} 3 -Li 2 O -based glass and / or _{B 2 O 3 -RO-Al 2} O 3 -Li 2 O system containing _Al 2 _{O 3} It is more preferably glass.

The _{SiO 2 -RO-Al 2 O 3} -Li 2 O -based _{glass, SiO 2 -CaO-Al 2 O} 3 -Li 2 O -based _{glass, SiO 2 -SrO-Al 2 O} 3 -Li 2 O -based glass, SiO _2- BaO-Al ₂ O _{3 -Li 2} O-based glass, SiO ₂ -CaO-SrO-Al ₂ O _{3 -Li 2} O-based glass, SiO _2- BaO-CaO-Al ₂ O _{3 -Li 2} O-based _{glass, SiO 2 -SrO-BaO-Al} 2 O 3 -Li 2 O -based _glass, such as _{SiO 2 -CaO-SrO-BaO-} Al 2 O 3 -Li 2 O system glass.

B ₂ O ₃ as the _{-RO-Al 2 O 3 -Li 2} O -based _{glass, B 2 O 3 -CaO-Al} 2 O 3 -Li 2 O -based _{glass, B 2 O 3 -SrO-Al} 2 O 3 - li ₂ O-based _{glass, B 2 O 3 -BaO-Al} 2 O 3 -Li 2 O -based _{glass, B 2 O 3 -CaO-SrO} -Al 2 O 3 -Li 2 O -based _glass, B ₂ O 3 -BaO _{-CaO-Al 2 O 3 -Li 2} O -based _{glass, B 2 O 3 -SrO-BaO} -Al 2 O 3 -Li 2 O -based _{glass, B 2 O 3 -CaO-SrO} -BaO-Al 2 O 3 - Examples _{include Li 2} O-based glass.

Among these, SiO _2- BaO-CaO-Al ₂ O _{3 -Li 2} O-based glass is preferable.

When using the _{SiO 2 -BaO-CaO-Al 2} O 3 -Li 2 O -based glass as the lithium-containing glass, and with the _{SiO 2 -BaO-CaO-Al 2} O 3 -Li 2 O system a whole glass 100 parts by weight Occasionally, _{the content of SiO 2} is 25 parts by mass or more and 45 parts by mass or less, the content of BaO is 20 parts by mass or more and 40 parts by mass or less, the content of CaO is 10 parts by mass or more and 30 parts by mass or less, and Al ₂ O ₃ It is preferable that the content is 1 part by mass or more and 10 parts by mass or less, Li ₂ O is a substantial balance of the lithium-containing glass, and _{the content of Li 2} O is 10 parts by mass or more and 30 parts by mass or less.

By _{setting the content of SiO 2} to 25 parts by mass or more, it becomes easy to improve the chemical stability of the second dielectric layer. By _{setting the content of SiO 2} to 45 parts by mass or less, low-temperature sintering becomes easy. By setting the BaO content to 20 parts by mass or more, the insulation reliability of the second dielectric layer is improved. By setting the BaO content to 40 parts by mass or less, the insulation reliability and Q value of the second dielectric layer are improved. By setting the CaO content to 10 parts by mass or more, the insulation reliability of the second dielectric layer is improved. By setting the CaO content to 30 parts by mass or less, the insulation reliability and Q value of the second dielectric layer are improved. By _{setting the content of Al 2} O ₃ to 1 part by mass or more, it becomes easy to improve the chemical stability of the second dielectric layer. By _{setting the content of Al 2} O ₃ to 10 parts by mass or less, low temperature sintering becomes easy. Note that the Li ₂ O is a substantial remainder of the lithium-containing _glass, SiO _2, BaO and _{SiO 2 -BaO-CaO-Al 2} O 3 -Li 2 overall O-based glass as 100 parts by weight, CaO, Al _{It means that the total content of 2} O ₃ and Li ₂ O is 95 parts by mass or more.

The content ratio of the lithium-containing glass is 2.0% by mass or more and 10.0% by mass or less with respect to a total of 100% by mass of the second principal component and the second subcomponent A. If the content ratio of the lithium-containing glass is too small, the low-temperature sinterability tends to decrease. On the other hand, if the content ratio of the lithium-containing glass is too large, the Q value tends to decrease.

In addition, zinc oxide may be contained as the second subcomponent A. However, in the second dielectric layer, assuming that the content ratio of zinc oxide to 100% by mass of the second main component is C2, C2 is smaller than the content ratio of zinc oxide (C1) to 100% by mass of the first main component.

C2 is not particularly limited as long as it is smaller than C1, but C2 is preferably 2.0% by mass or less, and more preferably 0.5% by mass or less. C2 may be 0% by mass. When C2 is larger than 0% by mass, the zinc oxide contained in the second dielectric layer preferably contains zinc oxide derived from the first dielectric layer. In other words, it is preferable that zinc oxide contained in a region other than the second dielectric layer (for example, the first dielectric layer) is diffused into the second dielectric layer and contained in the second dielectric layer. When such mutual diffusion occurs between the first dielectric layer and the second dielectric layer, the adhesion between the first dielectric layer and the second dielectric layer is improved.

Such mutual diffusion is likely to occur by making the content ratio of zinc oxide in the raw material of the first dielectric layer different from the content ratio of zinc oxide in the raw material of the second dielectric layer. However, usually, mutual diffusion does not proceed until the content ratio of zinc oxide in the raw material of the first dielectric layer and the content ratio of zinc oxide in the raw material of the second dielectric layer become the same.

Therefore, in order to make C2 smaller than C1, for example, the content ratio of zinc oxide in the raw material of the second dielectric layer may be lower than the content ratio of zinc oxide in the raw material of the first dielectric layer.

On the other hand, when the content ratio of zinc oxide in the raw material of the second dielectric layer is higher than the content ratio of zinc oxide in the raw material of the first dielectric layer, the zinc oxide contained in the second dielectric layer is the first. It becomes easy to move toward the dielectric layer, and a region (boundary reaction layer) in which zinc oxide is segregated tends to be formed at the interface between the first dielectric layer and the second dielectric layer. When such a boundary reaction layer is formed, the relative permittivity εr of the first dielectric layer tends to be significantly lower than the relative permittivity originally possessed by the first dielectric layer. When the relative permittivity εr of the first dielectric layer decreases, it tends to be difficult to miniaturize the electronic component, and the degree of freedom in material design decreases.

On the other hand, when the content ratio of zinc oxide in the raw material of the second dielectric layer is lower than the content ratio of zinc oxide in the raw material of the first dielectric layer, the first dielectric layer and the second dielectric are used. Since the boundary reaction layer is not formed between the layers, the relative permittivity εr of the first dielectric layer is unlikely to decrease.

When the content ratio of zinc oxide in the raw material of the first dielectric layer and the content ratio of zinc oxide in the raw material of the second dielectric layer are the same, mutual diffusion is unlikely to occur. As a result, the adhesion between the first dielectric layer and the second dielectric layer is lowered, and the resistance to the plating solution, flux, etc. is lowered. Therefore, the plating solution, flux, and the like tend to invade the interface between the first dielectric layer and the second dielectric layer.

Further, by containing manganese oxide as the second subcomponent A, it becomes easy to improve the low temperature sinterability of the second dielectric layer. Manganese oxide may be contained. However, in the second dielectric layer, the content ratio of manganese oxide is 2.0% by mass or less in terms of MnO with respect to 100% by mass of the second main component. If the content of manganese oxide is too large, the Q value of the second dielectric layer tends to decrease. The content ratio of manganese oxide is preferably 1.5% by mass or less, more preferably 1.0% by mass or less in terms of MnO. On the other hand, from the viewpoint of low-temperature sinterability, the content ratio of manganese oxide with respect to 100% by mass of the second main component is preferably 0.05% by mass or more in terms of MnO.

The method of measuring the content ratio of C1 and manganese oxide in the first dielectric layer and the content ratio of C2 and manganese oxide in the second dielectric layer is to measure the average concentration of elements contained in the dielectric layer. Any method that can be quantified will do. In the present embodiment, a portion having a predetermined volume is cut out from the first dielectric layer and the second dielectric layer of the laminated electronic component, each cut out portion is dissolved, and the dissolved liquid is ICP-MS (inductively coupled plasma). Quantitative analysis by mass spectrometry) method. Using the obtained analysis results, the content ratio of zinc oxide (C1) and manganese oxide to 100% by mass of the first main component, the content ratio of zinc oxide to 100% by mass of the second main component (C2), and The content ratio of manganese oxide can be calculated.

In the present embodiment, the portion cut out from the first dielectric layer is preferably a portion sandwiched between the electrodes. Therefore, since the portion cut out from the first dielectric layer contains not only the components constituting the first dielectric layer but also the components constituting the electrode, zinc oxide can be used without considering the components constituting the electrode. The content ratio (C1) and the content ratio of manganese oxide are calculated.

Further, it is preferable that the portion cut out from the second dielectric layer is a portion separated from the electrode by a predetermined distance and does not include the electrode. Therefore, the portion cut out from the second dielectric layer contains only the components constituting the second dielectric layer.

Further, whether or not the boundary reaction layer is formed between the first dielectric layer and the second dielectric layer may be a method capable of evaluating the difference in the composition of these layers. In the present embodiment, in the reflected electron image of the scanning electron microscope (SEM), the interface between the first dielectric layer and the second dielectric layer has a contrast different from that of the first dielectric layer and the second dielectric layer. The presence or absence of the boundary reaction layer is determined based on whether or not the region having the region appears.

Specifically, when the thickness of the region having a contrast different from that of the first dielectric layer and the second dielectric layer in the stacking direction of the first dielectric layer and the second dielectric layer is less than 1 μm. , It is judged that the boundary reaction layer is not formed, and if it is 1 μm or more, it is judged that the boundary reaction layer is formed.

By containing titanium oxide as the second subcomponent A, it becomes easy to improve the moisture resistance of the second dielectric layer. Titanium oxide (TiO ₂ ) may be contained. The content ratio of titanium oxide is preferably 0.3% by mass or more and 3.0% by mass or less in terms of _{TiO 2 with} respect to 100% by mass of the second main component, and is 0.3% by mass or more and 2.0% by mass. More preferably, it is less than%. If the content of titanium oxide is too small, the moisture resistance tends to decrease. On the other hand, if the content of titanium oxide is too large, the low temperature sinterability tends to decrease.

By containing aluminum oxide as the second subcomponent A, it becomes easy to improve the moisture resistance of the second dielectric layer. Aluminum oxide (Al ₂ O ₃ ) may be contained. The content of aluminum oxide, the second principal component 100 weight%, preferably _Al 2 _{O 3} is converted 0.3 wt% to 3.0 wt% or less, 0.3 wt% 2. It is more preferably 0% by mass or less. If the content of aluminum oxide is too small, the moisture resistance tends to decrease. On the other hand, if the content of aluminum oxide is too large, the low temperature sinterability tends to decrease.

(2. Manufacturing method of laminated electronic components)
Next, as an example of the manufacturing method of the laminated electronic component, an example of the manufacturing method of the LC filter 1 shown in FIG. 1 will be described below.

The LC filter 1 can be manufactured by a known method. As a known method, for example, a green sheet to be a first dielectric layer and a green sheet to be a second dielectric layer are prepared, these green sheets are laminated to form a green laminate, and this is fired. Later, a method of manufacturing by forming an external electrode is exemplified. Hereinafter, the manufacturing method will be specifically described.

First, a starting material for the first dielectric layer and a starting material for the second dielectric layer are prepared. As the starting material, oxides of each metal or various compounds which are components constituting the first dielectric layer and the second dielectric layer by firing can be used. Examples of various compounds include carbonates, oxalates, nitrates, hydroxides, organic metal compounds and the like. In this embodiment, the starting material is preferably powder.

As the starting material for the first dielectric layer, a starting material for the first principal component, a starting material for the first subcomponent A, and a starting material for the first subcomponent B are prepared. Examples of the starting material of the first main component include barium carbonate, neodymium hydroxide, titanium oxide, magnesium oxide, and silicon oxide powders. Examples of the starting material for the first subcomponent A include zinc oxide, manganese carbonate, boron oxide, bismuth oxide, and cobalt oxide powders. Examples of the starting material for the first subcomponent B include lithium-containing glass and silver powders. Lithium-containing glass is obtained by mixing raw materials such as oxides constituting the lithium-containing glass, firing the glass, quenching the glass, and vitrifying the glass. Moreover, as a starting material of silver, in addition to silver alone, a compound which can become silver by calcining can be mentioned. Examples of the compound that can become silver by calcining include silver nitrate, silver oxide, silver chloride and the like.

First, each powder of barium carbonate, neodymium hydroxide, and titanium oxide as a starting material of the first main component is in the range of x, y, and z described above, which are the molar ratios in _{the composition formula xBaO · yNd 2} O ₃ · zTIO _2. Weigh and mix so that it is inside. The mixing may be a dry mixing or a wet mixing. Wet mixing can be performed using, for example, a ball mill using pure water, ethanol or the like as a solvent. The mixing time may be, for example, about 4 to 24 hours.

The mixture obtained by mixing is dried at preferably 100 to 200 ° C., more preferably 120 to 140 ° C. for about 12 to 36 hours, and then calcined. By this calcining, a BaO-Nd ₂ O _3- TiO _2- based composite oxide is synthesized. The calcination temperature is preferably 1100 to 1500 ° C, more preferably 1100 to 1350 ° C. The calcination time is preferably about 1 to 24 hours.

The synthesized BaO-Nd ₂ O _3- TIO _2- based composite oxide is pulverized into a powder and then dried. As a result, _{a powder of BaO-Nd 2} O _3- TiO _2- based composite oxide is obtained. The pulverization may be dry pulverization or wet pulverization. For example, it can be carried out using a ball mill using pure water, ethanol or the like as a solvent. The crushing time may be about 4 to 24 hours. The powder may be dried at a drying temperature of preferably 100 to 200 ° C., more preferably 120 to 140 ° C. for about 12 to 36 hours.

Next, when forsterite is contained in the first principal component, magnesium oxide and silicon oxide, which are raw materials for forsterite, are weighed in predetermined amounts, mixed, and calcined. The mixture of magnesium oxide and silicon oxide may be a dry mixture or a wet mixture. For example, it can be carried out using a ball mill using pure water, ethanol or the like as a solvent. The mixing time may be, for example, about 4 to 24 hours.

The mixture obtained by mixing is dried at preferably 100 to 200 ° C., more preferably 120 to 140 ° C. for about 12 to 36 hours, and then calcined. Forsterite is synthesized by this calcining. The calcination temperature is preferably 1100 to 1500 ° C, more preferably 1100 to 1350 ° C. The calcination time is preferably about 1 to 24 hours.

The synthesized forsterite crystals are crushed into powder and then dried. As a result, a powder of forsterite crystals is obtained. The pulverization may be dry pulverization or wet pulverization. For example, it can be carried out using a ball mill using pure water, ethanol or the like as a solvent. The crushing time may be, for example, about 4 to 24 hours. The powder may be dried at a drying temperature of preferably 100 to 200 ° C., more preferably 120 to 140 ° C. for about 12 to 36 hours.

Further, as a raw material for forsterite, commercially available forsterite may be used. For example, commercially available forsterite may be pulverized by the method described above and dried to obtain a powder of forsterite crystals.

By blending the obtained BaO-Nd ₂ O _3- TiO _2- based composite oxide powder and the forsterite crystal powder so that the volume ratio is within the above-mentioned range, the raw material of the first main component is used. Is obtained.

Next, if necessary, zinc oxide, manganese carbonate, boron oxide, bismuth oxide, and cobalt oxide are weighed in a predetermined ratio as starting materials for the first subcomponent A and mixed with the raw material for the first main component. And obtain the mixed raw material. The mixing may be dry mixing or wet mixing. For example, it can be carried out using a ball mill using pure water, ethanol or the like as a solvent. The mixing time may be, for example, about 4 to 24 hours.

The obtained mixed raw material is dried at a drying temperature of preferably 100 to 200 ° C., more preferably 120 to 140 ° C. for about 12 to 36 hours.

The mixed raw material after drying is calcined at a temperature equal to or lower than the firing temperature described later, for example, 700 to 800 ° C. for about 1 to 10 hours. By calcining at a temperature equal to or lower than the firing temperature in this way, it is possible to prevent the forsterite in the mixed raw material from melting. As a result, forsterite is contained as crystals in the first dielectric layer.

As described above, the first main component and the first main component are obtained by performing calcining and pulverization twice in total, at the time before mixing each raw material and at the time after mixing each raw material into a raw material mixed powder. 1 Sub-ingredient A can be mixed uniformly.

Subsequently, when the mixed raw material after calcining is crushed, a raw material containing silver as the first subcomponent B and a lithium-containing glass are added. After that, a drying process is performed.

The addition of the silver-containing raw material is not limited to the time of crushing, and may be carried out at the time of mixing before calcination. Further, the addition of the lithium-containing glass is not limited to the time of pulverization, and may be performed at the time of mixing before calcining.

The pulverization may be dry pulverization or wet pulverization. For example, it can be carried out using a ball mill using pure water, ethanol or the like as a solvent. The crushing time may be, for example, about 4 to 24 hours. The crushed powder may be dried at a treatment temperature of 100 to 200 ° C., preferably 120 to 140 ° C. for about 12 to 36 hours.

In this way, the raw material for the first dielectric layer is obtained.

As the starting material for the second dielectric layer, a starting material for the second principal component, a starting material for the second auxiliary component A, and a starting material for the second auxiliary component B are prepared. Examples of starting materials for the second principal component include magnesium oxide and silicon oxide. Examples of the starting material for the second subcomponent A include alkaline earth metal carbonate, copper oxide, boron oxide, zinc oxide, manganese carbonate, titanium oxide, and aluminum oxide. Lithium-containing glass is exemplified as a starting material for the second subcomponent B. Lithium-containing glass is obtained by mixing raw materials such as oxides constituting the lithium-containing glass, firing the glass, quenching the glass, and vitrifying the glass.

First, the raw material powder of magnesium oxide and the raw material powder of silicon oxide are weighed in predetermined amounts and then mixed to obtain a mixture. The mixing may be a dry mixing or a wet mixing. For example, mixing is performed using a solvent such as pure water or ethanol in a mixing / dispersing machine such as a ball mill. In the case of a ball mill, the mixing time is about 4 to 24 hours.

The obtained mixture is preferably dried at 100 ° C. or higher and 200 ° C. or lower, more preferably 120 ° C. or higher and 140 ° C. or lower for about 12 to 36 hours, and then heat-treated (temporarily baked). Forsterite crystals are obtained by this calcining. The calcination temperature is preferably 1100 ° C. or higher and 1500 ° C. or lower, and preferably 1100 ° C. or higher and 1350 ° C. or lower. The calcination time is preferably about 1 hour to 24 hours.

The synthesized forsterite crystals are crushed into powder and then dried. As a result, forsterite crystal powder is obtained. This forsterite crystal powder is used as a raw material powder for the second principal component. The pulverization may be dry pulverization or wet pulverization. For example, wet pulverization is performed using a solvent such as pure water or ethanol in a ball mill. The crushing time is not particularly limited, and forsterite crystal powder having a desired average particle size may be obtained, and the crushing time may be, for example, about 4 hours to 24 hours. The forsterite crystal powder is preferably dried at a drying temperature of 100 ° C. or higher and 200 ° C. or lower, more preferably 120 ° C. or higher and 140 ° C. or lower, for about 12 hours or longer and 36 hours or shorter.

In order to increase the effect of forsterite crystals, it is necessary to reduce the raw material components of unreacted magnesium oxide and silicon oxide contained in forsterite. Therefore, when preparing a raw material mixed powder in which magnesium oxide and silicon oxide are mixed, it is preferable to mix magnesium oxide and silicon oxide so that the number of moles of magnesium is twice the number of moles of silicon.

The forsterite crystal powder is not limited to the method for synthesizing forsterite crystals from the raw material powder of magnesium oxide and the raw material powder of silicon oxide, and commercially available forsterite may be used. In this case, commercially available forsterite may be pulverized in the same manner as described above and dried to obtain forsterite crystal powder.

Subsequently, the obtained forsterite crystal powder and, if necessary, alkaline earth metal carbonate, boron oxide, copper oxide, zinc oxide, manganese carbonate, titanium oxide, and oxidation, which are raw materials for the second subcomponent A, are used. After weighing each powder of aluminum in a predetermined amount, these are mixed. The second subcomponent A may be added as an impurity in the forsterite crystal powder.

The mixing may be dry mixing or wet mixing. For example, it can be carried out by a mixing method using a solvent such as pure water or ethanol with a mixing / dispersing machine such as a ball mill. The mixing time may be about 4 hours or more and 24 hours or less.

The mixed powder is dried at a drying temperature of preferably 100 ° C. or higher and 200 ° C. or lower, more preferably 120 ° C. or higher and 140 ° C. or lower, for about 12 hours or longer and 36 hours or shorter.

The dried mixed powder is heat-treated (temporarily baked) at, for example, 700 ° C. or higher and 850 ° C. or lower for about 1 hour or more and 10 hours or less. By performing the calcining at a temperature equal to or lower than the firing temperature in this way, it is possible to prevent the forsterite in the raw material mixed powder from melting, and the forsterite in the form of crystals can be contained in the dielectric layer.

Lithium-containing glass, which is the second subcomponent B, is added to the mixed powder after calcination, mixed and pulverized, and then dried. The pulverization may be dry pulverization or wet pulverization. The crushing time may be about 4 hours or more and 24 hours or less. The mixed powder after pulverization may be dried at a treatment temperature of preferably 80 ° C. or higher and 200 ° C. or lower, more preferably 100 ° C. or higher and 140 ° C. or lower for about 12 hours or more and 36 hours or less.

By doing so, the second principal component and the second subcomponent are uniformly mixed, and a raw material for the second dielectric layer having a uniform material can be obtained.

In the present embodiment, the lithium-containing glass is added to the powder obtained by mixing the forsterite crystal powder and the raw material of the second subcomponent A and then heat-treating the lithium-containing glass. It is not limited to. The lithium-containing glass may be added, for example, at the stage of mixing the forsterite crystal powder and the raw material of the second subcomponent A (the stage before the heat treatment).

Next, the obtained raw material powder of the first dielectric layer and the raw material powder of the second dielectric layer are made into a paint to prepare a paste for the first dielectric layer and a paste for the second dielectric layer.

The paste for the first dielectric layer and the paste for the second dielectric layer may be an organic paint obtained by kneading a raw material powder and an organic vehicle, or may be a water-based paint.

The inner conductor paste is prepared by kneading a conductive material composed of, for example, silver or a silver alloy with the above-mentioned organic vehicle.

Next, the paste for the second dielectric layer is made into a sheet by a doctor blade method or the like to form a second dielectric green sheet.

Next, a coil conductor as an internal conductor is formed on the second dielectric green sheet produced above. To form the coil conductor, the paste for the inner conductor is formed on the second dielectric green sheet by a method such as screen printing. The coil conductor formation pattern may be appropriately selected according to the circuit configuration of the LC filter and the like.

Next, a through hole is formed in the coil conductor on the second dielectric green sheet. The through holes are filled with the paste for the inner conductor.

Subsequently, the paste for the first dielectric layer is made into a sheet by a doctor blade method or the like to form a first dielectric green sheet. Further, if necessary, an internal electrode as an internal conductor is formed on the first dielectric green sheet. The internal electrode may be formed by forming a paste for the internal conductor by a method such as screen printing.

Next, each of the green sheets produced above is laminated to form a green laminate.

In the present embodiment, in the green laminate, a plurality of second dielectric green sheets on which the coil conductor forming the inductance portion is formed are laminated, and an internal electrode forming the capacitor portion is formed on the plurality of second dielectric green sheets. It is manufactured by laminating a plurality of 1-dielectric green sheets, and further laminating a plurality of second dielectric green sheets on which a coil conductor constituting an inductance portion is formed.

Next, the obtained green laminate is fired. The firing temperature is preferably in the range of 800 to 1100 ° C, more preferably in the range of 800 to 1000 ° C.

Next, the fired laminate (sintered body) is subjected to end face polishing by, for example, barrel polishing or sandblasting, and then external electrode paste is applied to both side surfaces of the sintered body, dried, and then baked. The paste for an external electrode can be prepared by kneading a conductive material such as silver and the above-mentioned organic vehicle. The external electrodes formed in this way are preferably electroplated with Cu—Ni—Sn, Ni—Sn, Ni—Au, Ni—Ag or the like.

The LC filter manufactured in this way is mounted on a printed circuit board or the like by soldering or the like, and is used in various electronic devices and the like.

(3. Modification example)
In the above-described embodiment, the case where the laminated electronic component according to the present embodiment is an LC filter has been described, but the laminated electronic component according to the present embodiment is not limited to the LC filter, and the above-mentioned first dielectric layer and the above-mentioned first dielectric layer and Any electronic component having a second dielectric layer may be used. Specifically, the laminated electronic component according to this embodiment is suitably used for a high frequency device. Examples of high-frequency devices include capacitors, low-pass filters, band-pass filters, diplexers, duplexers, couplers, baluns, and the like.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments, and may be modified in various ways within the scope of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.

(Experiment 1)
(Preparation of raw material for first dielectric layer)
_{Barium carbonate (BaCO 3} ), neodymium hydroxide (Nd (OH) ₃ ), titanium oxide (TiO ₂ ), magnesium oxide (MgO) and silicon oxide (MgO) are used as raw materials for the first main component contained in the first dielectric layer. The powder of SiO ₂ ) was prepared. Further, as raw materials for the first subcomponent contained in the first dielectric layer, zinc oxide (ZnO), boron oxide (B ₂ O ₃ ), cobalt oxide (CoO), manganese carbonate (MnCO ₃ ), calcium carbonate (CaCO). ₃ ), bismuth oxide (Bi ₂ O ₃ ), silver (Ag) and lithium-containing glass A powders were prepared. Lithium-containing glass A _{is SiO 2 -BaO-CaO-Li 2} O -based crystalline glass, softening point 560 ° C., a glass transition point of 480 ° C. and crystallization point was 780 ° C..

The molar ratios x, y and z of xBaO · yNd ₂ O ₃ · zTIO ₂ obtained after calcination are x = 18.5 (mol%), y = 15.4 (mol%), z = 66.1 ( Each of the prepared powders was weighed so as to be (molar%).

Pure water was added to the weighed raw materials to prepare a slurry. This slurry was wet-mixed with a ball mill and then dried at 120 ° C. to obtain a powder. This powder was calcined in air for 4 hours at 1200 ° C., and the composition formulas were xBaO · yNd ₂ O ₃ · zTIO ₂ (x = 18.5 (mol%), y = 15.4 (mol%). ), Z = 66.1 (mol%)), and a BaO-Nd ₂ O _3- TiO _2- based composite oxide was obtained. Pure water was added to the obtained BaO-Nd ₂ O _3- TiO _2- based composite oxide to prepare a slurry. This slurry was pulverized by a ball mill and then dried at 120 ° C. to produce a powder of _{BaO-Nd 2} O _3- TiO _{2-based composite oxide.}

Subsequently, each powder prepared so that the number of moles of magnesium atoms was twice the number of moles of silicon atoms was weighed. Pure water was added to the weighed raw materials to prepare a slurry. This slurry was wet-mixed with a ball mill and then dried at 120 ° C. to obtain a powder. This powder was calcined in air for 3 hours at 1200 ° C. to obtain _{forsterite crystals (Mg 2} SiO _4). Pure water was added to the forsterite crystals to prepare a slurry. This slurry was pulverized with a ball mill and then dried at 120 ° C. to produce a forsterite crystal powder.

Next, with respect to the mixture obtained by mixing the obtained BaO-Nd ₂ O _3- TiO _2- based composite oxide powder and the forsterite crystal powder at the ratios shown in Table 1, the first subcomponent A After blending the raw materials ZnO, B ₂ O ₃ , CoO, MnCO ₃ and Bi ₂ O ₃ in the ratios shown in Table 1, pure water was further added to prepare a slurry.

This slurry was wet-mixed with a ball mill and then dried at 120 ° C. to obtain a raw material mixed powder. The obtained raw material mixed powder was calcined in air at 750 ° C. for 2 hours to obtain a calcined powder.

Silver and lithium-containing glass A, which are raw materials for the first subcomponent B, were added to the obtained calcined powder in the proportions shown in Table 1. Next, ethanol was added to the calcined powder containing silver and lithium-containing glass A to prepare a slurry. This slurry was wet-pulverized with a ball mill and then dried at 100 ° C. to obtain raw material powders A1 to A3 for the first dielectric layer.

To the obtained raw materials A1 to A3 of the first dielectric layer, 10% by mass of poly (ethyl methacrylate), which is an acrylic resin, was added as an organic binder to prepare a first dielectric paste. This second dielectric paste was sheet-molded by the doctor blade method to prepare a plurality of sheet-molded bodies. A sheet laminated molded body was produced by laminating a plurality of sheet molded bodies and then pressing them to form a substrate. The sheet laminated molded product was cut to a desired size to obtain chips. After chamfering the chips, they were fired at a firing temperature of 900 ° C. for 2 hours to prepare a second dielectric.

(Dielectric characteristic measurement)
The Q value and the relative permittivity εr of the sample for measuring the dielectric property of the first dielectric were measured according to a method called the cavity resonator perturbation method (JIS R1641). The measurement frequency was 2 GHz. The results are shown in Table 3.

(Preparation of raw material for second dielectric layer)
As a raw material for the second main component contained in the second dielectric layer, _{powders of magnesium oxide (MgO) and silicon oxide (SiO 2} ) were prepared. Further, as raw materials for the second subcomponent contained in the second dielectric layer, zinc oxide (ZnO), boron oxide (B ₂ O ₃ ), copper oxide (CuO), manganese carbonate (MnCO ₃ ), calcium carbonate (CaCO). ₃ ), titanium oxide (TiO ₂ ), aluminum oxide (Al ₂ O ₃ ), and lithium-containing glass B and C powders were prepared. The lithium-containing glasses B and C _are the _{SiO 2 -BaO-CaO-Al 2} O 3 -Li 2 O system crystallized glass, a glass transition point of the lithium-containing glass B is 480 ° C., the crystallization point is located at 780 ° C. The glass transition point of the lithium-containing glass C was 410 ° C., and the crystallization point was 490 ° C.

First, magnesium oxide and silicon oxide, which are the raw materials of the second main component, were weighed so that the number of moles of magnesium was twice the number of moles of silicon. Pure water was added to the weighed magnesium oxide and silicon oxide to prepare a slurry. When the entire slurry was 100 parts by mass, the total content of magnesium oxide and silicon oxide was 25 parts by mass.

The slurry was wet-mixed with a ball mill for 16 hours and then dried at 120 ° C. for 24 hours to obtain a mixed powder of magnesium oxide and silicon oxide. The mixed powder was calcined in air for 3 hours at 1200 ° C. to obtain forsterite crystals.

Pure water was added to the forsterite powder again to prepare a slurry. The content of the forsterite powder was set to 25 parts by mass when the entire slurry was 100 parts by mass. The slurry was pulverized in a ball mill for 16 hours and then dried at 120 ° C. for 24 hours to prepare a forsterite crystal powder.

Table Next, the forsterite crystal powder obtained, _ZnO as a raw material of the second auxiliary component, _{CuO, B} 2 O 3, the _{CaCO 3, MnCO 3, TiO 2} , Al 2 O 3 and Li-containing glass Raw materials B1 to B7 for the second dielectric layer were obtained by blending and mixing at the ratio shown in 2.

A second dielectric paste was prepared by adding 10% by mass of poly (ethyl methacrylate), which is an acrylic resin, as an organic binder to the raw materials B1 to B7 of the obtained second dielectric layer. This second dielectric paste was sheet-molded by the doctor blade method to prepare a plurality of sheet-molded bodies. A sheet laminated molded body was produced by laminating a plurality of sheet molded bodies and then pressing them to form a substrate. The sheet laminated molded product was cut to a desired size to obtain chips. After chamfering the chips, they were fired at a firing temperature of 900 ° C. for 2 hours to prepare a second dielectric.

Similar to the first dielectric, the Q value and the relative permittivity εr of the sample for measuring the dielectric properties of the second dielectric were measured according to a method called the cavity resonator perturbation method (JIS R1641). The measurement frequency was 2 GHz. The results are shown in Table 3.

(Composite chip)
A composite capacitor chip in which the first dielectric layer and the second dielectric layer shown in FIG. 2 are laminated using the raw materials A1 to A3 of the first dielectric layer and the raw materials B1 to B7 of the second dielectric layer. Comparative Examples 1 to 5 and Examples 1 to 4) were prepared as follows.

First, the second dielectric paste containing the raw materials B1 to B7 of the second dielectric layer was sheet-molded by the doctor blade method to prepare a plurality of sheet-molded bodies and laminated to form a sheet-laminated molded body.

A plurality of sheet molded bodies were produced by sheet molding the first dielectric paste containing the raw materials A1 to A3 of the first dielectric layer by the doctor blade method. An internal conductor paste was applied onto the sheet by screen printing on a part of the produced sheet molded product to form an internal electrode layer. A sheet molded body on which the internal electrode layer was formed and a sheet molded body on which the internal electrode layer was not formed were laminated to form a sheet laminated molded body.

The sheet laminated molded body of the first dielectric layer on which the internal electrode layer was formed was sandwiched between the sheet laminated molded bodies of the second dielectric layer to form a laminated body of composite capacitor chips.

The obtained laminate was fired at 900 ° C. for 2 hours to obtain a 1.6 × 0.8 × 0.6 mm sintered body. In order to form an external electrode at the end of the obtained sintered body, it was applied to both sides of the terminal using a commercially available Ag external electrode paste, dried at 120 ° C. for 15 minutes, and continuously fired in a continuous baking furnace (manufactured by LINDBERG). ) Was used to perform a baking treatment at 670 ° C. The chip on which the external electrode was formed was Cu-Ni-Sn plated with an electroplating apparatus, and each plating was performed until a predetermined film thickness was obtained to prepare a composite capacitor chip. The thickness of the capacitor portion was 40 μm, four internal electrode layers were formed in the capacitor portion, and three first dielectric layers were formed.

Subsequently, the obtained composite capacitor chips (Comparative Examples 1 to 5 and Examples 1 to 4) were evaluated for the presence or absence of a boundary reaction layer and the presence or absence of infiltration of a plating solution as follows.

The plated chip is broken with a pliers, and the broken boundary surface is observed with a scanning electron microscope (trade name: JSM-T300, manufactured by JEOL Datum Ltd.), and COMPO (composition) of the boundary surface after firing is observed. The image was taken at 2000 times and the thickness of the region different from the first dielectric layer and the second dielectric layer was measured. When the thickness of the region is less than 1 μm, it is determined that the boundary reaction layer is not formed, and when the thickness of the region is 1 μm or more, it is determined that the boundary reaction layer is formed. The results are shown in Table 3.

The plated chip was broken with pliers, and the broken boundary surface was observed with a scanning electron microscope (trade name: JSM-T300, manufactured by JEOL Ltd.), and the COMPO image of the boundary surface after firing (2000 times). ) Was photographed to confirm the presence or absence of the plating solution infiltrating the interface. The results are shown in Table 3.

With respect to the obtained capacitor chips (Comparative Examples 1 to 5 and Examples 1 to 4), the relative permittivity εr of the first dielectric layer was measured with an LCR meter. The results are shown in Table 3.

From Table 3, in Examples 1 to 4, the boundary reaction layer was not formed, the corrosion resistance was good, the decrease in the relative permittivity εr of the first dielectric layer could be suppressed, and in each of the first and second dielectrics. It was confirmed that a high Q value could be obtained.

(Experiment 2)
The raw materials for the first dielectric layer and the second dielectric layer were prepared in the same manner as in Experiment 1 except that the raw materials for the second subcomponent were blended in the ratios shown in Tables 4, 6 and 8, and these were prepared. A composite capacitor chip was made using this. In addition, the same evaluation as in Experiment 1 was performed on the first dielectric, the second dielectric, and the composite capacitor chip. The results are shown in Tables 5, 7 and 9.

From Tables 5, 7 and 9, the same results as in Experiment 1 were obtained.

(Experiment 3)
The raw materials for the first dielectric layer and the second dielectric layer were prepared in the same manner as in Experiment 1 except that the raw materials for the first subcomponent were blended in the proportions shown in Table 10, and a composite capacitor chip was prepared using these. Made. In addition, the same evaluation as in Experiment 1 was performed on the first dielectric, the second dielectric, and the composite capacitor chip. The results are shown in Table 11.

From Table 11, the same results as in Experiment 1 were obtained.

Subsequently, with respect to the 15 composite capacitor chips of Example 3 and the 15 composite capacitor chips of Comparative Example 1, the first dielectric portion A (0.8 mm × 0.05 mm × 0) shown in FIG. 2 from the first dielectric layer. .4 mm) and the second dielectric portion B (0.8 mm × 0.05 mm × 0.4 mm) shown in FIG. 2 were cut out from the second dielectric layer. The first dielectric portion A contained an internal electrode layer. The second dielectric portion B was separated from the outermost inner electrode layer of the first dielectric layer by 0.15 mm in the stacking direction and did not include the inner electrode layer.

An ICP-MS analyzer (Agilent 8900ICP-QQQ) was used after adding nitrate and hydrofluoric acid to each of the cut out first dielectric portion A and second dielectric portion B, dissolving them with a microwave, and diluting them. The amount of Zn, the amount of Mn, the amount of Mg, and the amount of Nd in the first dielectric portion A and the second dielectric portion B were measured using the mixture.

For the first dielectric portion A, the amount of the first main component (BaO-Nd ₂ O _3- TiO ₂ + Mg ₂ SiO ₄ ) is estimated from the amount of Nd and the amount of Mg, and oxidation is performed from the amount of Zn with respect to the amount of the first main component. The zinc content ratio (C1) was calculated, and the manganese oxide content ratio was calculated from the Mn amount with respect to the first main component amount.

For the second dielectric portion B, the amount of the second main component (Mg ₂ SiO ₄ ) is estimated from the amount of Mg, and the zinc oxide content ratio (C2) is calculated from the amount of Zn with respect to the amount of the second main component. The content ratio of manganese oxide was calculated from the amount of Mn with respect to the amount of two main components.

In the composite chip of Example 3, C1 was 3.2% by mass and C2 was 0.08% by mass. Therefore, C1> C2. On the other hand, in the composite chip of Comparative Example 1, C1 was 5.1% by mass and C2 was 10% by mass. Therefore, C1 <C2.

Further, in the composite chip of Example 3, the content ratio of manganese oxide in the first dielectric layer was 0.4% by mass, and the content ratio of manganese oxide in the second dielectric layer was 0.3% by mass. .. On the other hand, in the composite chip of Comparative Example 1, the content ratio of manganese oxide in the first dielectric layer was 0.4% by mass, and the content ratio of manganese oxide in the second dielectric layer was 0.0% by mass. ..

1 ... LC filter 10 ... Capacitor part 11 ... First dielectric layer 20 ... Inductance part 21 ... Second dielectric layer

Claims (9)

A first dielectric layer having a first principal component containing barium oxide, neodymium oxide, and titanium oxide,
An electronic component comprising a second dielectric layer having a second principal component containing forsterite.
In the first dielectric layer, when the content ratio of zinc oxide with respect to 100% by mass of the first principal component is C1, C1 is 5.0% by mass or less in terms of ZnO.
In the second dielectric layer, when the content ratio of zinc oxide with respect to 100% by mass of the second main component is C2, C2 is smaller than C1.
In the first dielectric layer, the content ratio of manganese oxide to 100% by mass of the first main component is 2.0% by mass or less in terms of MnO, and in the second dielectric layer, 100% by mass of the second main component. A laminated electronic component in which the content ratio of manganese oxide to% is 2.0% by mass or less in terms of MnO. The laminated electronic component according to claim 1, wherein C2 is 2.0% by mass or less. The laminated electronic component according to claim 1 or 2, wherein the first principal component further has forsterite. The laminated electronic component according to any one of claims 1 to 3, wherein the first dielectric layer and the second dielectric layer further have lithium-containing glass. The second dielectric layer further contains an alkaline earth metal oxide, boron oxide and copper oxide, and the content ratio of the alkaline earth metal oxide to 100% by mass of the second main component is 0.2 in RO conversion. Mass% or more and 4.0 mass% or less,
The content of the boron oxide to the second principal component 100 weight% is at _B 2 _{O 3} 3.0 wt% to 0.2 wt% in terms of the following,
The laminated electronic component according to any one of claims 1 to 4, wherein the content ratio of the copper oxide to 100% by mass of the second main component is 0.5% by mass or more and 3.0% by mass or less in terms of CuO. The softening point of the lithium-containing glass contained in the first dielectric layer is 570 ° C. or lower, and the crystallization point of the lithium-containing glass contained in the second dielectric layer is 500 ° C. or lower.
In the first dielectric layer, when the first dielectric layer does not contain silver, the lithium content is contained in a total of 100% by mass of the first main component, the first main component, and the components excluding the lithium-containing glass. The glass content is 2.0% by mass or more and 10.0% by mass or less.
In the first dielectric layer, when the first dielectric layer contains silver, the said is based on 100% by mass of the total of the first main component, the first main component, the lithium-containing glass, and the components excluding silver. The content ratio of lithium-containing glass is 2.0% by mass or more and 10.0% by mass or less.
In the second dielectric layer, the content ratio of the lithium-containing glass to 100% by mass in total of the second main component, the second main component, and the components excluding the lithium-containing glass is 2.0% by mass or more. The laminated electronic component according to claim 4 or 5, which is 0% by mass or less. The second dielectric layer further has titanium oxide, and the content ratio of the titanium oxide with respect to 100% by mass of the second main component is 0.3% by mass or more and 3.0% by mass or less in terms of _{TiO 2.} The laminated electronic component according to any one of 1 to 6. The second dielectric layer further contains aluminum oxide, and the content ratio of the aluminum oxide with respect to 100% by mass of the second main component is 0.3% by mass or more and 3.0% by mass or less in terms of _{Al 2} O _3. The laminated electronic component according to any one of claims 1 to 7. When barium oxide, neodymium oxide, titanium oxide contained in the first principal component and forsterite are represented by the composition formula {α (BaO · Nd ₂ O ₃ · TiO ₂ ) + β ( ₂ MgO · SiO 2)}. ,
The laminated electron according to any one of claims 3 to 8, wherein α and β indicate a volume ratio and satisfy the relationship of 35% by volume ≤ α ≤ 65% by volume, 35% by volume ≤ β ≤ 65% by volume, and α + β = 100. parts.

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