JP5733572B2 - Ceramic electronic component and method for manufacturing ceramic electronic component - Google Patents

Description

The present invention is ceramic electronic component, and relates to a manufacturing method of a ceramic electronic component, and more particularly, Cu principal component and the co-fired with the conductive material has been used a ferrite ceramic composition capable LC, such as composite component The present invention relates to a ceramic electronic component and a manufacturing method thereof.

  In recent years, ceramic electronic components have been widely used in various fields. For example, LC composite components are widely used as filter circuits for removing noise generated from electronic devices such as mobile phones and laptop computers.

  There are various types of LC composite parts. For example, Patent Document 1 discloses a capacitor portion in which dielectric layers and capacitor electrodes (capacitor electrode layers) are alternately stacked, and a magnetic layer and a coil conductor (coil). Spiral coil), and coil portions alternately stacked so that the coil conductors are connected between the layers, and these two portions are overlapped, and one end of the coil conductor of the capacitor portion and one end of the coil conductor of the coil portion And an LC composite component in which the capacitor portion and the coil portion are connected in series have been proposed.

  Further, this Patent Document 1 describes that a dielectric layer of a capacitor portion is formed of a magnetic material using a dielectric constant of a magnetic material itself, and further, Pd is used for a capacitor electrode and a coil conductor which are internal electrodes. It is described that a heat-resistant metal such as Ag-Pd is used.

  That is, in the LC composite part, it is desirable to manufacture by simultaneously firing the dielectric layer and the magnetic layer from the viewpoint of obtaining good productivity. In this case, the dielectric layer and the magnetic layer are formed. If the materials are different, structural defects such as delamination (delamination) and cracks may occur during simultaneous firing due to the difference in shrinkage behavior of these material types.

  Therefore, in Patent Document 1, by utilizing the dielectric constant of the magnetic material, the dielectric layer is formed of the same material as the magnetic layer, so that a structural defect is generated even if the capacitor portion and the coil portion are simultaneously fired. I'm trying to avoid that happening.

Japanese Utility Model Publication No. 60-17895 (Claim 1, second column, line 19 to third column, line 13)

  In a ceramic electronic component such as an LC composite component, as described in Patent Document 1, a magnetic material layer and a dielectric layer are formed of the same material using the dielectric constant of the magnetic material itself, It is desirable to form the capacitive electrode and the coil conductor with the same material.

  However, when a noble metal material such as Pd or Ag-Pd is used for the coil conductor and the capacitor electrode as in Patent Document 1, the material cost becomes high.

  In addition, Ag is normally used as the coil conductor material of the coil component. However, if such Ag is used also as the capacitor electrode material of the capacitor portion, migration may occur and a short circuit or the like may occur. In other words, when Ag is used for the capacitor electrode of the capacitor portion, if it is left for a long time in a high-humidity environment, migration occurs where the Ag is ionized and moves on the dielectric layer. There is a possibility that a short circuit or the like may occur, and it is difficult to obtain high reliability.

  Therefore, it is desirable to use a Cu-based material mainly composed of Cu, which is low in resistance, excellent in conductivity, and cheaper than Ag, as the capacitive electrode and the coil conductor.

However, from the relationship between the equilibrium oxygen partial pressure of Cu—Cu ₂ O and the equilibrium oxygen partial pressure of Fe ₂ O ₃ —Fe ₃ O ₄ , there is a region where Cu and Fe ₂ O ₃ coexist at a high temperature of 800 ° C. or higher. It is known not to exist.

That is, at a temperature of 800 ° C. or higher, when firing is performed with an oxygen partial pressure set in an oxidizing atmosphere that maintains the state of Fe ₂ O ₃ , Cu is also oxidized to produce Cu ₂ O. On the other hand, when firing is performed with an oxygen partial pressure set in a reducing atmosphere that maintains the state of Cu metal, Fe ₂ O ₃ is reduced to produce Fe ₃ O ₄ .

Since there is no region where Cu and Fe ₂ O ₃ coexist in this way, Fe ₂ O ₃ is reduced to Fe ₃ O ₄ when fired in a reducing atmosphere in which Cu does not oxidize. There is a risk that electrical characteristics will deteriorate.

The present invention has been made in view of such circumstances, and a ferrite porcelain composition capable of securing insulation and obtaining good electrical characteristics even when simultaneously fired with a metal wire mainly composed of Cu. and to provide a method of manufacturing LC ceramic electronic component such as a composite part, and the ceramic electronic component having a use for the high reliability.

The present inventors conducted extensive research on a ferrite material having a spinel crystal structure represented by the general formula X ₂ O ₃ .MeO (X is Fe, Mn, Me is Zn, Cu, Ni). Even if the Cu-based material and the ferrite material are simultaneously fired by making the blending amount of Fe ₂ O ₃ and Mn ₂ O ₃ into a specific range after setting the molar amount to 5 mol% or less, the desired good It has been found that it is possible to obtain insulating properties, and thereby it is possible to obtain a ceramic electronic component having good electrical characteristics.

The present invention has been made on the basis of such knowledge, and a ceramic electronic component according to the present invention includes a coil portion in which a coil conductor is embedded in a magnetic portion, and a capacitor in which a capacitive electrode is embedded in a dielectric portion. The coil conductor and the capacitive electrode are formed of a conductive material mainly composed of Cu, and the magnetic body part and the dielectric part are at least Fe, Mn, It is formed of a ferrite porcelain composition containing Zn and Ni. The ferrite porcelain composition has a Cu content molar amount of 0 to 5 mol% in terms of CuO, and Fe is converted into Fe ₂ O ₃ . molar content x mol% when converted, and the molar content Ymol% when the converted to _{Mn 2 O 3 Mn (x,} y) when expressed in, (x, y) is, a (25, 1), B (4 , 1), C (47, 7.5), D (45, 7.5), E (45, 10), F (35, 10), G (35, 7.5), and H (25, 7.5).

In the ceramic electronic component of the present invention, the coil part is formed by alternately laminating a plurality of magnetic body layers constituting the magnetic body part and a plurality of coil pattern parts constituting the coil conductor, It is preferable that a plurality of dielectric layers constituting the dielectric part and a plurality of electrode pattern parts constituting the capacitive electrode are alternately laminated, and further, the coil conductor and the capacitive electrode, and the magnetic part And the dielectric part are preferably fired simultaneously.

The ceramic electronic component according to the present invention includes a component body in which a coil conductor and a capacitive electrode are embedded in a magnetic body, and a capacitance is formed between the coil conductor and the capacitive electrode. A ferrite porcelain composition, wherein the coil conductor and the capacitive electrode are made of a conductive material mainly composed of Cu, and the magnetic body portion contains at least Fe, Mn, Zn, and Ni. The ferrite porcelain composition has a Cu content molar amount of 0 to 5 mol% in terms of CuO, and Fe is Fe. ₂ O ₃ Mole content xmol% when converted to Mn, and Mn as Mn ₂ O ₃ When the content molar amount ymol% in terms of (x, y) is expressed as (x, y), A (25,1), B (47,1), C (47,7.5) ), D (45, 7.5), E (45, 10), F (35, 10), G (35, 7.5), and H (25, 7.5) It is characterized by.

In the ceramic electronic component of the present invention, it is preferable that the component body has the capacitive electrode sandwiched between the coil conductors, and the coil conductor and the capacitive electrode and the magnetic body portion are simultaneously provided. It is preferable to be fired.

As a result of further diligent research by the present inventors, it is preferable to contain ZnO in the ferrite porcelain composition magnet from the viewpoint of obtaining even better characteristics, but the ZnO content exceeds 33 mol%. It has been found that the Curie point Tc is lowered, and the guarantee of operation at a high temperature is impaired, leading to a decrease in reliability.

That is, in the ceramic electronic component of the present invention, it is preferable that the ferrite porcelain composition has a molar content of Zn of 33 mol% or less in terms of ZnO.

Furthermore, from the research results of the present inventors, it was found that the ZnO content is preferably 6 mol% or more in consideration of the permeability μ of ferrite.

  That is, in the ceramic electronic component of the present invention, it is preferable that the ferrite porcelain composition has a molar content of Zn of 6 mol% or more in terms of ZnO.

Moreover, it is preferable that the ceramic electronic component of the present invention is fired in an atmosphere that is equal to or lower than the equilibrium oxygen partial pressure of Cu—Cu ₂ O.

A method for manufacturing a ceramic electronic component according to the present invention is 0 to 5 mol% molar content of Cu in terms of CuO, and the molar content x mol% when converted to Fe in _Fe 2 _{O 3} , And when Mn is converted to Mn ₂ O ₃ and the content molar amount ymol% is represented by (x, y), (x, y) is A (25,1), B (47, 1) , C (47, 7.5), D (45, 7.5), E (45, 10), F (35, 10), G (35, 7.5), and H (25, 7.5) ) Is a calcining step in which a Fe compound, a Mn compound, a Cu compound, a Zn compound, and a Ni compound are weighed so as to be a region surrounded by (), and these weighed materials are mixed and then calcined to produce a calcined powder. And a ceramic thin layer body production process for producing a ceramic thin layer body from the calcined powder, and Cu as a main component A conductive film forming step of forming a conductive film on the semi-thick thin layer body, and a laminate forming step of stacking the ceramic thin layer body on which the conductive film is formed in a predetermined order to form a stacked body; And a firing step of firing the laminated body in a firing atmosphere of Cu-Cu ₂ O equal to or lower than the equilibrium oxygen partial pressure and simultaneously firing the ceramic thin layer body and the conductive film.

According to the ceramic electronic component of the present invention, a ceramic electronic component comprising a coil portion in which a coil conductor is embedded in a magnetic portion and a capacitor portion in which a capacitive electrode is embedded in a dielectric portion, the coil conductor And the capacitor electrode is made of a conductive material mainly composed of Cu, and the magnetic part and the dielectric part are made of a ferrite porcelain composition containing at least Fe, Mn, Zn, and Ni . the ferrite ceramic composition, the molar amount of Cu is 0 to 5 mol% in terms of CuO, and the molar content x mol% when converted to Fe in _Fe 2 _{O 3,} and Mn Mn ₂ When the content molar amount ymol% in terms of O ₃ is represented by (x, y), since (x, y) is in the specific region surrounded by the points A to H described above, the Cu-based material And ferrite material Be co-fired with and fees, Cu is Ru can be suppressed from the Fe ₂ O ₃ or the oxide is reduced. As a result, a desired insulating property can be ensured without causing a decrease in the specific resistance ρ, and a ceramic electronic component having a good magnetic property can be obtained. In addition, since a conductive material containing Cu as a main component is also used for the capacitor electrode, it is possible to avoid migration from occurring in the capacitor portion as in the case of an Ag-based material. Therefore, a good insulation resistance can be obtained even if left for a long time under high humidity, and a ceramic electronic component such as an LC composite component having high reliability can be obtained.

Specifically, it is possible to obtain a good insulating property having a specific resistance ρ of 10 ⁷ Ω · cm or more. This makes it possible to obtain a desired ceramic electronic component having good electrical characteristics such as impedance characteristics.

  In addition, by setting the molar content of Zn to 33 mol% or less in terms of ZnO, a ceramic electronic component that can ensure a sufficient Curie point and guarantees operation under conditions of high temperature during use. Can be obtained.

  Furthermore, it is possible to ensure good magnetic permeability by converting the Zn content to 6 mol% or more in terms of ZnO.

  Further, according to the ceramic electronic component of the present invention, the coil conductor and the capacitor electrode are embedded in the magnetic layer in a form in which the capacitor electrode is sandwiched between the coil conductors, and between the coil conductor and the capacitor electrode. Even when the capacitance is formed, the coil conductor and the capacitance electrode are formed of a conductive material mainly composed of Cu, and the magnetic layer is made of the ferrite porcelain composition according to any one of the above. Since it is formed, it is possible to avoid the occurrence of migration as well as the desired good electrical and magnetic properties even when co-fired with a Cu-based material, as described above. Ceramic electronic parts such as composite parts can be obtained.

In addition, by firing in an atmosphere below the equilibrium oxygen partial pressure of Cu—Cu ₂ O, a conductive material containing Cu as a main component is used for the coil conductor and the capacitor electrode at the same time as the magnetic layer and the dielectric layer. Even when fired, Cu can be sintered without being oxidized, and a ceramic electronic component such as an LC composite component having good moisture resistance and high reliability can be obtained.

Moreover, according to the manufacturing method of the ceramic electronic component of the present invention, the molar content of Cu is 0 to 5 mol% in terms of CuO, and the molar content x mol in terms of Fe is converted to Fe ₂ O _3. %, And a content range ymol% when Mn is converted to Mn ₂ O ₃ is represented by (x, y), (x, y) is a specific range surrounded by the points A to H described above. A calcining step in which a Fe compound, a Mn compound, a Cu compound, a Zn compound, and a Ni compound are weighed so as to satisfy the conditions, and after mixing these weighed products, calcining to prepare a calcined powder; Forming a ceramic thin layer body from powder, forming a conductive film having a predetermined pattern of Cu as a main component on the ceramic thin layer body, and forming the conductive film. The ceramic thin layer Laminated in a predetermined order, simultaneously with the stack forming step of forming a laminated body, firing the laminate in the firing atmosphere of the equilibrium oxygen partial pressure of a Cu-Cu 2 _O, and said conductive film and said ceramic green sheet And a firing step of firing, Fe is reduced even if the ceramic green sheet and the conductive film containing Cu as a main component are fired at the same time in a firing atmosphere equal to or lower than the equilibrium oxygen partial pressure of Cu—Cu ₂ O. Therefore, a ceramic electronic component having good insulation and high reliability can be obtained.

It is a diagram showing the composition range of _Fe 2 _{O 3} and _Mn 2 _{O 3} of the ferrite ceramic composition according to the present invention. 1 is a perspective view showing an embodiment (first embodiment) of an LC composite component as a ceramic electronic component according to the present invention. FIG. 3 is a cross-sectional view of FIG. 2. It is an equivalent circuit diagram of the first embodiment. It is a disassembled perspective view which shows the principal part of the said 1st Embodiment. It is a perspective view of 2nd Embodiment of LC composite component as a ceramic electronic component which concerns on this invention. It is sectional drawing of FIG. It is a disassembled perspective view which shows the principal part of the said 1st Embodiment. It is sectional drawing of 3rd Embodiment of LC composite component as a ceramic electronic component which concerns on this invention. It is an equivalent circuit diagram of the third embodiment. It is a disassembled perspective view which shows the principal part of the said 3rd Embodiment. It is a schematic diagram which shows the internal structure of 4th Embodiment of LC composite component as a ceramic electronic component which concerns on this invention. It is the equivalent circuit schematic of the said 4th Embodiment. It is a disassembled perspective view which shows the principal part of the said 4th Embodiment. 3 is a cross-sectional view of a specific resistance measurement sample manufactured in Example 1. FIG. It is the figure which showed the insertion loss of this invention sample produced in Example 2 with the comparative example sample outside the scope of the present invention. It is a figure which shows the insertion loss of this invention sample produced in Example 3. FIG.

  Next, an embodiment of the present invention will be described in detail.

The ferrite porcelain composition used for the ceramic electronic component of the present invention has a spinel crystal structure represented by the general formula X ₂ O ₃ .MeO, and is Fe ₂ O ₃ , Mn ₂ which is at least a trivalent element compound. O ₃ and ZnO and NiO which are divalent element compounds are contained, and CuO which is a divalent element compound is contained as necessary.

Specifically, in the present ferrite porcelain composition, the molar content of CuO is 0 to 5 mol%, and each molar content of Fe ₂ O ₃ and Mn ₂ O ₃ is Fe _{2 as} shown in FIG. x mol% of molar content of O _3, when the Ymol% of molar content of _Mn 2 _{O 3,} is a (x, y) is hatched portion X of a region surrounded by points A~ point H, the balance It is made of ZnO or NiO.

  Here, each point (x, y) of point A to point H indicates the following molar content.

A (25,1), B (47,1), C (47,7.5), D (45,7.5), E (45,10), F (35,10), G (35, 7.5), and H (25,7.5)
Next, the reason why the molar amounts of CuO, Fe ₂ O ₃ , and Mn ₂ O ₃ are in the above range will be described in detail.

(1) CuO content molar amount In Ni-Zn ferrite, the inclusion of CuO having a melting point as low as 1026 ° C in the ferrite porcelain composition enables firing at a lower temperature and improves the sinterability. Can do.

On the other hand, in the case of simultaneously firing a Cu-based material containing Cu as a main component and a ferrite material, Cu is easily oxidized to form Cu ₂ O when fired in an air atmosphere. It is necessary to bake in the atmosphere.

However, when firing in such a reducing atmosphere, if the molar content of CuO exceeds 5 mol%, CuO in the ferrite raw material is reduced and the amount of Cu ₂ O generated increases, and therefore the specific resistance ρ is reduced. There is a risk of lowering.

  Therefore, in the present embodiment, the blending amount is adjusted so that the molar amount of CuO is 5 mol% or less, that is, 0 to 5 mol%.

(2) Respective molar amounts of Fe ₂ O ₃ and Mn ₂ O _{3 By} reducing the amount of Fe ₂ O ₃ from the stoichiometric composition and substituting part of Fe with Mn, Mn ₂ O ₃ is contained. Therefore, it is possible to avoid a decrease in specific resistance ρ, and to improve insulation.

That is, in the case of the spinel crystal structure (general formula X ₂ O ₃ · MeO), the stoichiometric composition is the ratio of X ₂ O ₃ (X: Fe, Mn) to MeO (Me: Ni, Zn, Cu). Is 50:50, and X ₂ O ₃ and MeO are usually blended so as to have a substantially stoichiometric composition.

When co-firing a Cu-based material containing Cu as a main component and a ferrite material, Cu is easily oxidized to form Cu ₂ O when fired in an air atmosphere, so that reducing properties such that Cu does not oxidize. It is necessary to bake in the atmosphere. On the other hand, when Fe ₂ O ₃ which is the main component of the ferrite material is fired in a reducing atmosphere, Fe ₃ O ₄ is generated. Therefore, it is necessary to fire Fe ₂ O _{3 in} an oxidizing atmosphere.

However, as described in the section “Problems to be Solved by the Invention”, from the relationship between the equilibrium oxygen partial pressure of Cu—Cu ₂ O and the equilibrium oxygen partial pressure of Fe ₃ O ₄ —Fe ₂ O ₃ , 800 It is known that there is no region where Cu metal and Fe ₂ O ₃ coexist when firing at a temperature of 0 ° C. or higher.

However, Mn ₂ O ₃ becomes a reducing atmosphere at a higher oxygen partial pressure than Fe ₂ O ₃ in the temperature range of 800 ° C. or higher. Therefore, at an oxygen partial pressure equal to or lower than the equilibrium oxygen partial pressure of Cu—Cu ₂ O, Mn ₂ O ₃ becomes a strongly reducing atmosphere as compared with Fe ₂ O ₃ , and therefore Mn ₂ O ₃ is preferentially reduced and burned. The result can be completed. In other words, since _{the Mn} 2 _{O 3} it is preferentially reduced as compared with _{Fe 2 O 3, Fe 2 O} 3 it is possible to complete the baking process before being reduced to _Fe 3 _{O 4.}

Thus, by reducing the content molar amount of Fe ₂ O ₃ from the stoichiometric composition, by containing Mn ₂ O ₃ which is the same trivalent element compound in the ferrite ceramic composition, Cu—Cu ₂ Sintering is completed before Fe ₂ O ₃ is reduced because Mn ₂ O ₃ is reduced preferentially even if Cu-based material and ferrite material are co-fired below the equilibrium oxygen partial pressure of O Cu metal and Fe ₂ O ₃ can coexist more effectively. And it can avoid that specific resistance (rho) falls by this, and can improve insulation.

However, when the content molar amount of Fe ₂ O ₃ is less than 25 mol%, the content molar amount of Fe ₂ O ₃ is excessively decreased, and on the contrary, the specific resistance ρ is lowered, so that desired insulation cannot be ensured.

In addition, when the molar amount of Mn ₂ O ₃ is less than 1 mol%, the molar amount of Mn ₂ O ₃ is excessively reduced, so that Fe ₂ O ₃ is easily reduced to Fe ₃ O ₄ and the specific resistance ρ Decreases, and sufficient insulation cannot be secured.

In addition, even when the molar content of Fe ₂ O ₃ exceeds 47 mol%, the molar content of Fe ₂ O ₃ becomes excessive and Fe ₂ O ₃ is easily reduced to Fe ₃ O ₄ , and the specific resistance ρ is reduced. It is lowered and sufficient insulation cannot be secured.

Further, even when the molar content of Mn ₂ O ₃ exceeds 10 mol%, a sufficiently large specific resistance ρ cannot be obtained, and insulation cannot be ensured.

Furthermore, when the content molar amount of Fe ₂ O ₃ is 25 mol% or more and less than 35 mol%, and when the content molar amount of Fe ₂ O ₃ is 45 mol% or more and less than 47 mol%, Mn ₂ If the content molar amount of O ₃ exceeds 7.5 mol%, the specific resistance ρ is reduced on the contrary, and desired insulation cannot be secured.

Therefore, in the present embodiment, the molar amounts of Fe ₂ O ₃ and Mn ₂ O ₃ are adjusted so that the molar amounts are in a region surrounded by points A to H in FIG.

Incidentally, the molar content of ZnO and NiO ferrite ceramic composition is not limited in _{particular, Fe 2 O 3, Mn 2} O 3, and be appropriately set according to the molar content of CuO However, it is preferable to blend so that ZnO: 6 to 33 mol% and NiO: the balance.

  That is, if the ZnO content exceeds 33 mol%, the Curie point Tc is lowered, and there is a possibility that the operation at high temperature may not be guaranteed. Therefore, the ZnO content is preferably 33 mol% or less.

  On the other hand, ZnO has an effect of contributing to the improvement of the magnetic permeability μ, but in order to exert such an effect, the molar amount of ZnO needs to be 6 mol%.

  Accordingly, the molar content of ZnO is preferably 6 to 33 mol%.

Thus, the present ferritic ceramic composition is 0 to 5 mol% molar content of Cu in terms of CuO, and the molar content x mol% when converted to Fe in _Fe 2 _{O 3,} and Mn When the content molar amount ymol% when converted to Mn ₂ O ₃ is represented by (x, y), (x, y) is in a specific range surrounded by the points A to H described above. Even if co-firing with the Cu-based material, it is possible to ensure desired insulation without causing a decrease in specific resistance ρ.

Specifically, it is possible to obtain a good insulating property having a specific resistance ρ of 10 ⁷ Ω · cm or more. This makes it possible to obtain a desired ceramic electronic component having good electrical characteristics such as impedance characteristics.

  Moreover, by converting the Zn content molar amount to 6 to 33 mol% in terms of ZnO, it has a good magnetic permeability and can secure a sufficient Curie point, under conditions where the temperature during use is high. It is possible to obtain a ceramic electronic component in which the operation is guaranteed.

  Next, a ceramic electronic component using the ferrite porcelain composition will be described in detail with reference to FIGS.

  FIG. 2 is a perspective view showing an embodiment (first embodiment) of an LC composite component as a ceramic electronic component according to the present invention, and FIG. 3 is a cross-sectional view of FIG.

  The first embodiment shows a lumped constant type vertically wound T-type LC composite component.

  That is, in this LC composite component, the component body 1 has a capacitor portion 2 interposed between a pair of coil portions 3a and 3b. The coil portions 3a and 3b include coil conductors 5a and 5b and magnetic layers 6a and 6b in which the coil conductors 5a and 5b are embedded. The capacitor portion 2 includes a capacitive electrode 7 and the capacitive electrode 7. And a dielectric layer 8 embedded therein. The coil conductors 5a and 5b of the coil parts 3a and 3b are electrically connected to the first and second external electrodes 4a and 4b formed at both ends of the component element body 1, and the capacitance of the capacitor part 2 The electrode 7 is electrically connected to third and fourth external electrodes 4c and 4d formed at the center of the side surface of the component element body 1.

  FIG. 4 is a circuit diagram showing an equivalent circuit of the LC composite component.

  That is, the LC composite component forms a T-type circuit configuration by the inductance L1 provided by the coil portion 3a, the inductance L2 provided by the coil portion 3b, and the capacitance C provided by the capacitor portion 2. ing.

  In the first embodiment, the coil conductors 5a and 5b and the capacitor electrode 7 are formed of a Cu-based material containing Cu as a main component, and not only the magnetic layers 6a and 6b but also the dielectric layer 8 is formed. The ferrite ceramic composition of the present invention described above is used. That is, the dielectric layer 8 utilizes the dielectric constant of the ferrite porcelain composition, and the dielectric layer 8 is formed with the ferrite porcelain composition.

As a result, Cu does not oxidize or Fe ₂ O ₃ is reduced, and it has desired good electrical and magnetic properties. Specifically, the specific resistance ρ can be improved to 10 ⁷ Ω · cm or more, and an LC composite component suitable for noise absorption in a specific frequency range can be obtained.

  In addition, since the Cu-based material is used for the capacitor electrode 7, it is possible to avoid the occurrence of migration in the capacitor portion 2 as in the case of the Ag-based material. Insulation resistance can be obtained, and an LC composite component having high reliability can be obtained.

  FIG. 5 is an exploded perspective view of the component body 1.

  Hereinafter, the manufacturing method of the LC composite component will be described in detail with reference to FIG.

First, Fe ₂ O ₃ , ZnO, NiO, and, if necessary, CuO are prepared as ceramic raw materials. Then, CuO is a 0~5mol%, _Fe 2 _{O 3} and _Mn 2 _{O 3} are weighed each ceramic raw materials to meet specific region surrounded by points A~ point H.

  Next, these weighed products are put in a pot mill together with pure water and cobblestones such as PSZ (partially stabilized zirconia) balls, sufficiently mixed and pulverized wet, evaporated and dried, and then temporarily heated at a temperature of 700 to 800 ° C. for a predetermined time. Bake.

  Next, these calcined powders are again put into a pot mill together with an organic binder such as polyvinyl butyral, an organic solvent such as ethanol and toluene, and PSZ balls, and sufficiently mixed and pulverized to produce a ceramic slurry.

  Next, the ceramic slurry is formed into a sheet shape using a doctor blade method or the like, and a magnetic ceramic green sheet (ceramic thin layer body; hereinafter, simply referred to as “magnetic sheet”) 9a to 9a. 9m is produced.

  Next, among the magnetic sheets 9a to 9m, the magnetic sheets 9d to 9i are formed with via holes at predetermined positions using a laser processing machine so that they can be electrically connected to each other.

  Next, a conductive paste containing Cu as a main component (hereinafter referred to as “Cu paste”) is prepared. Then, screen printing is performed using the Cu paste, coil patterns 10a to 10d or capacitance patterns 11a to 11c (conductive film) are formed on the magnetic sheets 9d to 9j, and via holes are filled with the Cu paste. Via conductors 12a to 12f are produced.

  The coil portions 10a and 10d formed on the magnetic sheet 9d and the magnetic sheet 9j are connected to the first and second external electrodes 4a and 4b so as to be electrically connected to the lead portions 10a ′, 10d 'is formed. The capacitor pattern 11b formed on the magnetic sheet 9g is formed with a lead portion 11b 'so as to be electrically connected to the third and fourth external electrodes 4c and 4d, and the magnetic sheet 9g. A land portion 13 is formed around the via hole 12d.

  Next, these magnetic sheets 9d to 9j are laminated, and the exterior magnetic sheets 9a to 9c and 9k to 9m are arranged on the upper and lower main surfaces. After these are pressed and pressed, they are cut to a predetermined size. A laminated molded body is produced. As a result, the coil patterns 10a to 10d are electrically connected via the via conductors 12a to 12f to form the coil conductors 5a and 5b after sintering, and the first and first coil conductors 10a 'and 10d' are used to form the first and first coil patterns. The second external electrodes 4a and 4b can be electrically connected. Further, the magnetic sheet 9g is electrically insulated from the coil patterns 10a to 10d, and after sintering, the capacitor part 2 is formed by the magnetic sheets 9f to 9h, and the third and fourth through the lead part 11b '. The external electrodes 4c and 4d can be electrically connected.

Next, an atmosphere such as the molded laminate Cu is not oxidized, was sufficiently degreased at a predetermined temperature, so that the equilibrium oxygen partial pressure of a _{Cu-Cu 2 O N 2 -H} 2 -H 2 O Is supplied to a firing furnace whose atmosphere is adjusted with a mixed gas of, and fired at 900 to 1050 ° C. for a predetermined time, whereby the coil conductors 5a and 5b are embedded in the magnetic layers 6a and 6b, and the capacitor electrode 7 is a dielectric layer. The component base body 1 embedded in 8 is obtained.

  Next, a conductive paste for external electrodes mainly composed of Cu or the like is applied to both end portions and side surface center portions of the component element body 1, dried, and then baked at a temperature of about 900 ° C. External electrodes 4a to 4d are formed, whereby the above-described LC composite component is manufactured.

In this manner, in the present first embodiment, a 0 to 5 mol% molar content of Cu in terms of CuO, and the molar content x mol% when converted to Fe in _Fe 2 _{O 3,} and When the content molar amount ymol% when Mn is converted to Mn ₂ O ₃ is represented by (x, y), (x, y) satisfies the specific region surrounded by the points A to H described above. Fe compound, Mn compound, Cu compound, Zn compound, and Ni compound are respectively weighed, mixed with these weighed products, and calcined to prepare a calcined powder, and the calcined powder is magnetically processed. Magnetic sheet production step for producing body sheets 9a to 9m, and conductive pattern (conductive film) formation step for forming coil patterns 10a to 10d or capacitance patterns 11a to 11c having a predetermined pattern by applying Cu paste to the magnetic sheet. The magnetic sheet 9d~9j which the pattern is formed by laminating a predetermined order, and the laminate formation step of forming a molded laminate, the laminate molded in the firing atmosphere of the equilibrium oxygen partial pressure of a Cu-Cu 2 _O firing the body, wherein the magnetic sheet 9a~9m and the conductive pattern 10 a to 10 d, because it contains a firing step of co-firing and 11a~11c, Cu-Cu ₂ O firing atmosphere under equilibrium oxygen partial pressure of Even if the magnetic sheets 9a to 9m and the conductive patterns 10a to 10d and 11a to 11c are fired simultaneously, Cu is not oxidized or Fe is not reduced, and the insulation is good and the LC has high reliability. Composite parts can be obtained.

  FIG. 6 is a perspective view showing a second embodiment of an LC composite component as a ceramic electronic component according to the present invention, and FIG. 7 is a cross-sectional view of FIG.

  This second embodiment shows a lumped constant type laterally wound T-type LC composite component.

  That is, in this LC composite component, as in the first embodiment, the component body 15 has the capacitor portion 16 interposed between the pair of coil portions 17a and 17b. The coil portions 17a and 17b include coil conductors 20a and 20b and magnetic layers 21a and 21b in which the coil conductors 20a and 20b are embedded. The capacitor portion 16 includes a capacitive electrode 22 and the capacitive electrode. And a dielectric layer 23 in which 22 is embedded. The coil conductors 20a and 20b of the coil parts 17a and 17b are electrically connected to the first and second external electrodes 18a and 18b formed on the upper and lower surfaces of the component element body 1, and The capacitor electrode 22 is electrically connected to a third external electrode 18 c provided around the center of the side surface of the component body 15.

  The LC composite component also forms a T-type circuit configuration as in the first embodiment.

  Also in the second embodiment, the coil conductors 20a and 20b and the capacitor electrode 22 are formed of Cu, and not only the magnetic layers 21a and 21b but also the dielectric layer 23 of the ferrite porcelain composition of the present invention described above. It is formed of things.

As a result, as in the first embodiment, Cu is not oxidized or Fe ₂ O ₃ is not reduced, it has desired good electrical and magnetic characteristics, and migration does not occur. It becomes possible to obtain a ceramic electronic component having high reliability.

  Moreover, in the second embodiment, since the stray capacitance in the coil portions 17a and 17b can be reduced as compared with the first embodiment, an LC composite component with further reduced insertion loss can be obtained. Is possible.

  FIG. 8 is an exploded perspective view of the component body 15.

  Hereinafter, the manufacturing method of the LC composite component will be described in detail with reference to FIG.

  First, a calcined powder is produced by the same method as in the first embodiment, and then a ceramic slurry is produced.

  Next, the ceramic slurry is formed into a sheet using a doctor blade method or the like, and magnetic sheets 20a to 20q having a predetermined thickness are produced.

  Next, a laser processing machine is used so that the magnetic sheets 20a to 20q can be electrically connected, and via holes are formed at predetermined positions.

  Next, a Cu paste is prepared. And it screen-prints using this Cu paste, forms coil pattern 21a-21f or capacity | capacitance pattern 22a-22e on the magnetic material sheet 20d-20n, and is filled with a via hole with the said Cu paste, and via conductor 23a- 23q is produced.

  The capacitor patterns 22b and 22d formed on the magnetic sheets 20h and 20j are formed with lead portions 22b'22d 'so as to be electrically connected to the third external electrode 19.

  And these magnetic material sheets 20a-20q are laminated | stacked, it is made to pressurize and pressure-bond, and it cut | disconnects to a predetermined dimension, and produces a laminated molding. As a result, the coil patterns 21a to 21c and 20d to 20f are electrically connected via the via conductors 23d to 23m to form the coil conductors 20a and 20b after sintering, and the via conductors 23a to 23c and 23o to 23q are formed. The first and second external electrodes 18a and 18b can be electrically connected to each other. Further, the magnetic sheets 20h and 20j are electrically insulated from the coil patterns 21a to 21c and 20d to 20f, and after sintering, the capacitor portions 16 are formed by the magnetic sheets 20g to 20k, and the lead portions 22b 'and 22d' are formed. It is possible to conduct to the third external electrode 18c via the.

Next, an atmosphere such as the molded laminate Cu is not oxidized, was sufficiently degreased by heating, Cu-Cu ₂ O in such an equilibrium oxygen partial pressure under _N 2 _-H 2 _-H 2 O Is supplied to a firing furnace whose atmosphere is adjusted with a mixed gas of, and fired at 900 to 1050 ° C. for a predetermined time, whereby the coil conductors 20a and 20b are embedded in the magnetic layers 21a and 21b, and the capacitor electrode 22 is a dielectric layer. The component base body 15 embedded in 23 is obtained.

  Next, a conductive paste for external electrodes mainly composed of Cu or the like is applied to both end portions and side surface central portions of the component element body 1, dried, and then baked at 900 ° C. to form first to third external electrodes. 18a to 18c are formed, and thereby the above-described LC composite component is manufactured.

As described above, also in the second embodiment, the laminate is fired in a firing atmosphere having an equilibrium oxygen partial pressure of Cu—Cu ₂ O or less, and the ceramic green sheet and the conductive film are fired simultaneously. Similarly to the first embodiment, Cu is not oxidized and Fe is not reduced, and an LC composite component having good resistivity and high reliability with a specific resistance ρ of 10 ⁷ Ω · cm or more is obtained. be able to.

  In addition, since a Cu-based material is used for the capacitor electrode 22, it is possible to avoid migration and obtain an LC composite component having high reliability.

  Moreover, in the second embodiment, since the stray capacitance in the coil portions 17a and 17b can be reduced as compared with the first embodiment, an LC composite component with further reduced insertion loss can be obtained. Is possible.

  FIG. 9 is a cross-sectional view showing a third embodiment of an LC composite component as a ceramic electronic component according to the present invention.

  The third embodiment shows a lumped constant type π-type LC composite component.

  That is, in this LC composite component, the component body 30 has a coil portion 31 interposed between a pair of capacitor portions 32a and 32b. The capacitor portions 32a and 32b include capacitive electrodes 36a and 36b and dielectric layers 37a and 37b in which the capacitive electrodes 36a and 36b are embedded. The coil portion 31 includes a coil conductor 34 and the coil conductor. 34 is provided with a magnetic body 35 embedded therein. The capacitor electrodes 36a and 36b of the capacitor portions 32a and 32b are electrically connected to the first and second external electrodes 33a and 33b formed at both ends of the component body 30, and the coil conductor of the coil portion 31 is connected. 34 is electrically connected to third and fourth external electrodes (not shown) formed at the center of the side surface of the component body 30.

  FIG. 10 is a circuit diagram showing an equivalent circuit of the present LC composite component.

  That is, this LC composite component is a so-called LC capacitor in which the capacitance C1 provided by the capacitor portion 32a and the capacitance C2 provided by the capacitor portion 32b are connected in parallel via the inductance L provided by the coil portion 31. A π-type circuit configuration is formed.

  In the third embodiment, the coil conductor 34 and the capacitive electrodes 36a and 36b are formed of a Cu-based material, and not only the magnetic layer 35 but also the dielectric layers 37a and 37b are described above. It is formed of a porcelain composition.

As a result, as in the first and second embodiments, Cu is not oxidized and Fe ₂ O ₃ is not reduced, and it has desired good electrical and magnetic characteristics and migration occurs. Accordingly, it is possible to obtain a ceramic electronic component having high reliability.

  FIG. 11 is an exploded perspective view of the component body 30.

  Hereinafter, the manufacturing method of the LC composite component will be described in detail with reference to FIG.

  First, calcined powder is produced by the same method as in the first and second embodiments, and then ceramic slurry is produced.

  Next, the ceramic slurry is formed into a sheet using a doctor blade method or the like, and magnetic sheets 38a to 38p having a predetermined thickness are produced.

  Next, a laser processing machine is used so that the magnetic sheets 38h and 38i can be electrically connected, and via holes are formed at predetermined positions.

  Next, a Cu paste is prepared. Then, screen printing is performed using the Cu paste, capacitance patterns 39a to 39c and 39f to 39h are formed on the magnetic sheets 38d to 38f and 38k to 38m, and coil patterns 39d and 39e are formed on the magnetic sheets 38h and 3i. And the via hole is filled with the conductive paste to produce the via conductor 40.

  The capacitance patterns 39a to 39c and 39f to 39h and the coil patterns 39d and 39e are led out from the lead portions 39a 'to 39c', 39f 'to 39h' and 39d 'so as to be electrically connected to the external electrodes. , 39e 'are formed.

  And these magnetic material sheets 38d-38n are laminated | stacked, the magnetic material sheets 38a-38c and 38n-38p for exterior are arrange | positioned on the upper and lower both main surfaces, these are pressurized and crimped | bonded, and it cut | disconnects to a predetermined dimension after that. A laminated molded body is produced.

Next, an atmosphere such as the molded laminate Cu is not oxidized, was sufficiently degreased at a predetermined temperature, so that the equilibrium oxygen partial pressure of a _{Cu-Cu 2 O N 2 -H} 2 -H 2 O Is supplied to a firing furnace whose atmosphere is adjusted with a mixed gas of, and fired at 900 to 1050 ° C. for a predetermined time, whereby the capacitive electrodes 36a and 36b are embedded in the dielectric layers 37a and 37b, and the coil conductor 34 is a magnetic layer A component body 30 embedded in 35 is obtained.

  Next, the external electrode conductive paste mainly composed of Cu or the like is applied to both end portions and side surface central portions of the component element body 30, dried, and then baked at 900 ° C. to form first to fourth external electrodes. This forms the LC composite component described above.

As described above, also in the third embodiment, the laminated body is fired in a firing atmosphere that is equal to or lower than the equilibrium oxygen partial pressure of Cu—Cu ₂ O, and the ceramic green sheet and the conductive film are fired simultaneously. As in the first and second embodiments, Cu is not oxidized or Fe is reduced, and the specific resistance ρ is 10 ⁷ Ω · cm or more, and the LC composite has good insulation and high reliability. Parts can be obtained.

  Further, since the Cu-based material is used for the capacitive electrodes 36a and 36b, it is possible to avoid the occurrence of migration and to obtain an LC composite component having high reliability.

  FIG. 12 is an internal structure diagram showing a fourth embodiment of an LC composite component as a ceramic electronic component according to the present invention.

  The fourth embodiment shows a distributed constant type horizontally wound T-type LC composite component.

  That is, in this LC composite component, the component body 40 has the coil conductor 41 and the capacitor electrode 42 embedded in the magnetic layer 43 in such a manner that the capacitor electrode 42 is sandwiched between the coil conductors 41. Both ends of the coil conductor 41 are electrically connected to the first and second external electrodes 49a and 49b, and the capacitor electrode 42 is electrically connected to the third and fourth external electrodes (ground electrodes) 49c and 49d. It is connected to the.

  FIG. 13 is a circuit diagram showing an equivalent circuit of the present LC composite component.

  That is, in this LC composite component, the capacitive electrode 42 is arranged in a form along the coil conductor 41, and therefore, between the inductance L provided by the coil conductor 41 and the magnetic layer 43 and the capacitive electrode 42. A capacitance C is formed. Therefore, in this LC composite component, the inductance L provided by the coil conductor 41 and the magnetic layer 43 is continuously formed between the external electrodes 49a and 49b, and the substantially entire length of the coil conductor 41 to which the inductance L is provided. Therefore, since the capacitance C is continuously formed between the capacitance electrode 42 and the impedance matching between the input signal side and the output signal side, the high frequency characteristics capable of transmitting a desired signal waveform are excellent. It will be.

  Also in the fourth embodiment, the coil conductor 41 and the capacitor electrode 42 are formed of a Cu-based material, and the magnetic layer 43 is formed of the above-described ferrite porcelain composition of the present invention.

As a result, as in the first to third embodiments, Cu is not oxidized and Fe ₂ O ₃ is not reduced, and it has desired good electrical and magnetic properties and migration occurs. Accordingly, it is possible to obtain a ceramic electronic component having high reliability.

  FIG. 14 is an exploded perspective view of the component body 40.

  Hereinafter, the manufacturing method of the LC composite component will be described in detail with reference to FIG.

  First, calcined powder is produced by the same method as in the first to third embodiments, and then a ceramic slurry is produced.

  Next, the ceramic slurry is formed into a sheet using a doctor blade method or the like, and magnetic sheets 44a to 44j having a predetermined film thickness are produced.

  Next, using a laser processing machine, via holes are formed at predetermined positions of the magnetic sheets 44b to 44h.

  Next, a Cu paste is prepared. Then, screen printing is performed using the Cu paste, coil patterns 45a to 45f are formed on the magnetic sheets 44b, 44c, 44e, and 44g to 44i, and capacitance patterns 46a and 46b are formed on the magnetic sheets 44d and 44f. The via conductors 47a to 47i are formed by filling the via holes with the Cu paste.

  And these magnetic material sheets 44b-44i are laminated | stacked, the magnetic material sheet | seat 44a, 44j for exterior is arrange | positioned to upper and lower both main surfaces, these are pressurized and crimped | bonded, and it cuts to a predetermined dimension after that, and produces a laminated molding. To do.

Next, an atmosphere such as the molded laminate Cu is not oxidized, was sufficiently degreased at a predetermined temperature, so that the equilibrium oxygen partial pressure of a _{Cu-Cu 2 O N 2 -H} 2 -H 2 O Is supplied to a firing furnace whose atmosphere is adjusted with a mixed gas of, and fired at 900 to 1050 ° C. for a predetermined time, whereby the component body 40 in which the coil conductor 41 and the capacitor electrode 42 are embedded in the magnetic layer 43 is obtained.

  Next, the external electrode conductive paste mainly composed of Cu or the like is applied to both end portions and side surface central portions of the component element body 40, dried, and then baked at 900 ° C. to form first to fourth external electrodes. This forms the LC composite component described above.

As described above, also in the fourth embodiment, the laminated body is fired in a firing atmosphere that is equal to or lower than the equilibrium oxygen partial pressure of Cu—Cu ₂ O, and the ceramic green sheet and the conductive film are fired simultaneously. As in the first to third embodiments, Cu is not oxidized or Fe is not reduced, and the specific resistance ρ is 10 ⁷ Ω · cm or more, and the LC composite has good insulation and high reliability. Parts can be obtained.

  Further, since the capacitor electrode 42 is also formed of a Cu-based material, it is possible to avoid migration and obtain an LC composite component having high reliability.

  The present invention is not limited to the above embodiment. For example, in the above embodiment, the ceramic green sheets 9a to 9m are prepared from the calcined powder, but any ceramic thin layer body may be used. For example, a printing process is performed on a PET film to form a magnetic coating film. And you may form the coil pattern and capacitive pattern which are electrically conductive films on such a magnetic coating film.

  In the above embodiment, the coil pattern and the capacitance pattern are formed by screen printing. However, the method for manufacturing the conductive film is not particularly limited, and other methods such as plating, transfer, or sputtering are used. You may form by thin film formation methods, such as.

  Moreover, although the LC composite component has been described in the above embodiment, the present invention is not limited to these embodiments. Needless to say, the ferrite material can be widely used for simultaneous firing with the Cu-based material, and can be applied to other ceramic electronic components.

  Next, examples of the present invention will be specifically described.

Fe ₂ O ₃ , Mn ₂ O ₃ , ZnO, CuO, and NiO were prepared as ceramic raw materials, and these ceramic raw materials were weighed so that the molar content was as shown in Tables 1 to 3. . That is, 30 mol% of ZnO and 1 mol% of CuO were fixed, the molar amounts of Fe ₂ O ₃ and Mn ₂ O ₃ were varied, and each ceramic raw material was weighed so that the balance was NiO.

  Next, these weighed materials are put together with pure water and PSZ balls into a pot mill made of vinyl chloride, thoroughly mixed and pulverized in a wet manner, evaporated and dried, and then calcined at a temperature of 750 ° C. to obtain a calcined powder. It was.

  Next, this calcined powder was again put into a vinyl chloride pot mill together with a polyvinyl butyral binder (organic binder), ethanol (organic solvent), and PSZ balls, and sufficiently mixed and pulverized to obtain a ceramic slurry.

  Next, using a doctor blade method, the ceramic slurry was formed into a sheet shape so as to have a thickness of 25 μm, and this was punched into a size of 50 mm in length and 50 mm in width to produce a magnetic sheet.

  Next, a plurality of the magnetic sheets prepared in this way are stacked so that the total thickness is 1.0 mm, heated to 60 ° C., and pressed and pressed at a pressure of 100 MPa for 60 seconds, and then A ceramic molded body was obtained by cutting into a ring shape so that the outer diameter 20 was mm and the inner diameter was 12 mm.

Subsequently, the obtained ceramic molded body was heated and fully degreased. Then, after supplying a mixed gas of N ₂ —H ₂ —H ₂ O to the firing furnace to adjust the oxygen partial pressure to 6.7 × 10 ⁻² Pa, the ceramic molded body was put into the firing furnace, and 1000 Firing was performed at a temperature of 0 ° C. for 2 hours, thereby obtaining a ring-shaped sample.

This oxygen partial pressure 6.7 × 10 ⁻² Pa is the equilibrium oxygen partial pressure of Cu—Cu ₂ O at 1000 ° C., and the ceramic molded body is fired at the equilibrium oxygen partial pressure of Cu—Cu ₂ O for 2 hours. Thus, ring-shaped samples of sample numbers 1 to 104 were produced.

  And about each ring-shaped sample of sample numbers 1-104, an annealed copper wire is wound 20 turns, and an impedance analyzer (the E4991A made by Agilent Technologies) is used, an inductance is measured with a measurement frequency of 1 MHz, and the measured value is used. Permeability μ was determined.

  Next, Cu powder was mixed with an organic vehicle containing terpineol (organic solvent) and ethyl cellulose resin (binder resin), and kneaded with a three-roll mill, thereby preparing a Cu paste.

  Next, Cu paste was screen-printed on the surface of the magnetic material sheet to produce a conductive film having a predetermined pattern. Then, a predetermined number of magnetic sheets on which a conductive film is formed are laminated in a predetermined order, sandwiched between magnetic sheets on which a conductive film is not formed, crimped, and cut into a predetermined size to obtain a laminated molded body. It was.

Next, after fully degreasing the laminated molded body, a mixed gas of N ₂ —H ₂ —H ₂ O was supplied to the firing furnace to set the oxygen partial pressure to 6.7 × 10 ⁻² Pa (Cu—Cu at 1000 ° C. ₂ was adjusted to _O equilibrium oxygen partial pressure), after supplying the laminate molded body in a firing furnace and fired for two hours at a temperature of 1000 ° C., to obtain a ceramic sintered body in which internal electrodes are embedded.

  Next, this ceramic sintered body was put into a pot together with water, and the ceramic sintered body was subjected to barrel treatment using a centrifugal barrel machine, thereby obtaining a ceramic body.

And after applying the electroconductive paste for external electrodes which has Cu as a main component to the both ends of a ceramic body, and drying, it is 900 in the baking furnace which adjusted oxygen partial pressure to 4.3 * 10 < ^-3 > Pa. A baking process was performed at a temperature of 0 ° C. to prepare samples for specific resistance measurement of sample numbers 1 to 104. The oxygen partial pressure: 4.3 × 10 ⁻³ Pa is the equilibrium oxygen partial pressure of Cu—Cu ₂ O at a temperature of 900 ° C.

  The external dimensions of the specific resistance measurement sample were 3.0 mm in length, 3.0 mm in width, and 1.0 mm in thickness.

  FIG. 15 is a cross-sectional view of a specific resistance measurement sample. Internal electrodes 52 a to 52 d are embedded in the magnetic layer 53 so that the lead portions are staggered in the ceramic body 51, and the ceramic body 51. External electrodes 54a and 54b are formed on both end faces of the.

  Next, for the specific resistance measurement samples of sample numbers 1 to 104, a voltage of 50 V was applied to the external electrodes 54a and 54b for 30 seconds, and the current at the time of voltage application was measured. Then, the resistance was calculated from the measured value, and the logarithm logρ of the specific resistance (hereinafter referred to as “specific resistance logρ”) was calculated from the sample size.

  Tables 1 to 3 show the ferrite compositions and measurement results of sample numbers 1 to 104.

  Sample numbers 1 to 17, 22 to 25, 30 to 33, 39 to 41, 47 to 49, 55 to 57, 63 to 65, 71 to 73, 78 to 81, and 86 to 104 are hatched portions X in FIG. Therefore, the specific resistance logρ is less than 7, the specific resistance logρ is small, and a desired insulating property cannot be obtained.

  On the other hand, sample numbers 18 to 21, 26 to 29, 34 to 38, 42 to 46, 50 to 54, 58 to 62, 66 to 70, 74 to 77, and 82 to 85 are indicated by the hatched portion X in FIG. Since it is in the enclosed region, it was found that the specific resistance logρ is 7 or more, good insulation is obtained, and a practically sufficient value of 50 or more is obtained for the magnetic permeability μ.

As shown in Table 4, the ceramic raw material is within the scope of the present invention, with the molar content of Fe ₂ O ₃ being 44 mol%, the molar content of Mn ₂ O ₃ being 5 mol%, and the molar content of ZnO being 30 mol. %, CuO was varied, and the balance was NiO. Other than that, a ring-shaped sample Nos. 201 to 209 and a specific resistance measurement sample were prepared by the same method and procedure as in Example 1.

  Next, with respect to sample numbers 201 to 209, the specific resistance logρ and the magnetic permeability were measured by the same method and procedure as in Example 1.

  Table 4 shows the ferrite compositions and measurement results of sample numbers 201 to 209.

  In Sample Nos. 207 to 209, since the molar amount of CuO exceeds 5 mol%, the specific resistance logρ is less than 7 and the specific resistance logρ is small, so that the desired insulating properties cannot be obtained.

  On the other hand, 201 to 206 have a CuO content of 0 to 5 mol%, which is within the range of the present invention, so that the specific resistance logρ is 7 or more, good insulation is obtained, and the magnetic permeability μ is 210 or more. Good results were obtained.

As shown in Table 5, the molar content of Fe ₂ O ₃ is 44 mol%, the molar content of Mn ₂ O ₃ is 5 mol%, the molar content of CuO is 1 mol% within the scope of the present invention, and the molar content of ZnO A ring-shaped sample and samples for specific resistance measurement were prepared by the same method and procedure as in Example 1 except that the amount of the ceramic raw material was weighed so that the balance was NiO. .

  And about the sample numbers 301-309, the specific resistance log (rho) and the magnetic permeability were measured by the method and procedure similar to Example 1. FIG.

  For sample numbers 301 to 309, a vibrating sample magnetometer (VSM-5-15 manufactured by Toei Kogyo Co., Ltd.) was used, a 1T (Tesla) magnetic field was applied, and the temperature dependence of saturation magnetization was measured. . The Curie point Tc was determined from the temperature dependence of the saturation magnetization.

  Table 5 shows the ferrite compositions and measurement results of sample numbers 301 to 309.

  In Sample No. 309, since the molar content of ZnO exceeds 33 mol%, the specific resistance logρ and the permeability μ were good, but the Curie point Tc was 110 ° C., which was lower than other samples. I found out.

  In Sample Nos. 301 and 302, since the molar content of ZnO is less than 6 mol%, the specific resistance logρ and the Curie point Tc were good, but the magnetic permeability μ decreased to 20 or less.

  On the other hand, sample numbers 303 to 308 have a molar amount of ZnO of 6 to 33 mol%, and therefore, the Curie point Tc is 165 ° C. or higher and operation at a high temperature of about 130 ° C. can be obtained. It was also found that the magnetic permeability μ was 35 or more, and a practical magnetic permeability μ was obtained.

  From the above, it was confirmed that when the content molar amount of ZnO is increased, the magnetic permeability μ is increased, but when the amount is excessively increased, the Curie point Tc is decreased.

  Using a magnetic sheet having the same composition as Sample No. 1 produced in Example 1, Sample No. 203 produced in Example 2, and Sample No. 209, a vertically wound T-type LC composite component was produced (FIGS. 2 to 5). reference).

  For the magnetic sheets of Sample No. 1 and Sample No. 203, Cu was used for the coil conductor material and the capacitive electrode material, and samples No. 1 ′ and 203 ′ (vertically wound T-type LC composite parts) were produced.

  For the magnetic material sheet of sample number 209, Ag was used as the coil conductor material and the external electrode material, and a sample of sample number 209 ′ (vertically wound T-type LC composite part) was produced.

  That is, in order to produce the sample of sample number 209 ′, in addition to the Cu paste used in Examples 1 to 3, a conductive paste mainly composed of Ag (hereinafter referred to as “Ag paste”) was prepared.

  Samples Nos. 1 ′, 203 ′, and 209 ′ were prepared by the following procedure.

  First, using a laser processing machine, via holes were formed at predetermined locations on the magnetic sheets of sample numbers 1, 203 and 209.

  Next, screen printing was performed using Cu paste or Ag paste to form a coil pattern or a capacitance pattern on the magnetic sheet, and via holes were filled with the Cu paste or Ag paste to produce via conductors.

  Then, these magnetic sheets are laminated, and the outer magnetic sheets are arranged on the upper and lower main surfaces, and these are heated to 60 ° C. and pressed for 60 seconds at a pressure of 100 MPa, cut into predetermined dimensions, and a sample. Laminated molded bodies having numbers 1 ′, 203 ′ and 209 ′ were produced.

Next, for sample numbers 1 'and 203', after heating and degreasing sufficiently in an atmosphere in which Cu does not oxidize, N _{2-is set} so that the oxygen partial pressure becomes 6.7 × 10 ^-2 Pa. The mixture was supplied to a firing furnace whose atmosphere was adjusted with a mixed gas of H ₂ —H ₂ O and fired at a temperature of 1000 ° C. for 2 hours to obtain a component body.

Next, a conductive paste for an external electrode containing Cu as a main component was applied to both end portions and side surface center portions of the component element body, dried, and then the oxygen partial pressure was adjusted to 4.3 × 10 ⁻³ Pa. Baking treatment was performed at a temperature of 900 ° C. in a firing furnace, thereby forming first to fourth external electrodes. Next, electrolytic plating was performed to sequentially form a Ni film and a Sn film on the surfaces of the first to fourth external electrodes, thereby producing vertical winding T-type LC composite parts of sample numbers 1 ′ and 203 ′.

  On the other hand, for sample number 209 ', the external electrode conductive paste mainly composed of Ag is applied to both end portions and side surface central portions of the component body, dried, and then baked at a temperature of 750 ° C. in an air atmosphere. Processing was performed, thereby forming first to fourth external electrodes. After that, similarly to Sample Nos. 1 ′ and 203 ′, electrolytic plating is performed to sequentially form a Ni film and an Sn film on the surfaces of the first to fourth external electrodes, whereby the vertical winding of Sample No. 209 ′ is performed. A T-type LC composite part was produced.

  The external dimensions of each of the produced samples were 2.0 mm in length, 1.25 mm in width, and 0.9 mm in thickness.

  The specifications of the coil conductor and the capacitor of each sample were adjusted so that the measurement frequency was 1 MHz, the inductance L was about 0.3 μH, and the capacitance C was about 360 pF.

  Next, an electrometer (R8340A manufactured by Advantest Corp.) is used for each of the sample numbers 1 ′, 203 ′, and 209 ′, and the insulation resistance between the coil conductor external electrode and the capacitor external electrode, that is, between the terminals The insulation resistance logIR of was measured.

  Table 6 shows the ferrite composition and measurement results of the samples of sample numbers 1 ′, 203 ′, and 209 ′.

As apparent from Table 6, the insulation resistance logIR of Sample No. 1 ′ was as low as 3.1. This is because, in the ferrite composition, the molar amount of Fe ₂ O ₃ and Mn ₂ O ₃ is outside the range of the present invention, so Fe ₂ O ₃ is reduced to Fe ₃ O ₄ , and the insulation resistance logIR is lowered. It seems to have done.

On the other hand, Sample Nos. 203 ′ and 209 ′ have favorable results such that the insulation resistance logIR is 7.2 and 8.9 because the molar amounts of Fe ₂ O ₃ and Mn ₂ O ₃ are within the range of the present invention. It was. Sample No. 209 ′ was fired in the air, and the ferrite material was not reduced. Therefore, a satisfactory result was obtained for the insulation resistance logIR.

  Next, the insertion loss was measured for each sample No. 1 ′, 203 ′ and 209 ′ using a network analyzer (E5062A manufactured by Agilent Technologies).

  FIG. 16 shows the measurement results.

Sample No. 1 ′ was deteriorated in insertion loss compared to Sample Nos. 203 ′ and 209 ′. This is because the molar content of Fe ₂ O ₃ and Mn ₂ O ₃ is outside the range of the present invention, and as described above, Fe ₂ O ₃ is reduced to Fe ₃ O ₄ , and the resistance of the magnetic layer is reduced. It is thought that it was because.

  Next, 30 samples of sample numbers 203 ′ and 209 ′ were subjected to a humidity resistance load test by applying a DC voltage of 5 V under a high temperature and high humidity of 85 ° C. and 85% humidity. That is, for each sample, the insulation resistance was measured between terminals before the start of the test and after 250 hours, 500 hours, 1000 hours, and 2000 hours after the start of the test, and the insulation resistance logIR decreased by 20% or more compared to before the test. The sample was regarded as a defective product, and the number of the defective products was counted to evaluate the moisture resistance.

  Table 7 shows the measurement results.

  In Sample No. 209 ′, the number of defective products increased with time, and the defect occurrence rate reached 100% after 1000 hours. This is presumably because migration occurred and the resistance of the capacitor portion decreased because the capacitor electrode was formed of Ag.

  On the other hand, sample No. 203 'has a capacitor electrode made of Cu, so that no migration occurs and no defective product occurs after 2000 hours, and a highly reliable LC composite component can be obtained. I understood.

  Using a magnetic sheet having the same composition as Sample No. 203 produced in Example 2 and using Cu as the coil conductor material and the capacitive electrode material, a laterally wound T-type LC composite component was produced (Sample No. 203 ″) ( 6 to 8).

  That is, first, a laser processing machine was used at a predetermined location of the magnetic sheet of sample number 203, and a via hole was formed at the predetermined location.

  Next, screen printing was performed using a Cu paste, a coil pattern or an electrode pattern was formed on the magnetic material sheet, and a via hole was filled with the Cu paste to produce a via conductor.

  Then, these magnetic sheets are laminated, and the outer magnetic sheets are arranged on the upper and lower main surfaces, and these are heated to 60 ° C. and pressed for 60 seconds at a pressure of 100 MPa, cut into predetermined dimensions, and a sample. No. 203 ″ laminated molded body was produced.

Next, after heating and degreasing sufficiently in an atmosphere where Cu is not oxidized, a mixed gas of N ₂ —H ₂ —H ₂ O is used so that the oxygen partial pressure becomes 6.7 × 10 ⁻² Pa. It supplied to the baking furnace with which atmosphere was adjusted, and baked for 2 hours at the temperature of 1000 degreeC, and obtained the component element | base_body.

  Next, the Cu paste is applied to both end portions and side surface center portions of the component body and dried, and then baked at 900 ° C. to form first to fourth external electrodes, and then subjected to electrolytic plating, A Ni film and an Sn film were sequentially formed on the surfaces of the first to fourth external electrodes, thereby producing a vertically wound T-type LC composite part of sample number 203 ″.

The baking atmosphere was performed by adjusting the oxygen partial pressure to 4.3 × 10 ⁻³ Pa, which is the equilibrium oxygen partial pressure of Cu—Cu ₂ O at 900 ° C.

  The external dimensions of the manufactured sample were 2.0 mm in length, 1.25 mm in width, and 0.9 mm in thickness. The specifications of the coil conductor and the capacitor of each sample were adjusted so that the measurement frequency was 1 MHz, the inductance L was about 0.3 μH, and the capacitance C was about 360 pF.

  Next, with respect to sample number 203 ″, insertion loss was measured by the same method and procedure as in Example 2.

  FIG. 17 shows the measurement results.

  As can be seen from FIG. 17, the sample number 203 ″ has an improved insertion loss compared to the sample number 203 ′. This is because the sample number 203 ′ has a vertical winding structure, whereas the sample number 203 ″. This is probably due to the fact that the stray capacitance at the coil portion was further reduced because of the horizontal winding structure.

  Even when a conductive material containing Cu as a main component is used for a coil conductor or a capacitor electrode and these and a magnetic layer are fired at the same time, it has good insulation, good electrical characteristics, Ceramic electronic parts such as LC composite parts that can suppress the occurrence of migration can be realized.

2, 16, 32a, 32b Capacitor portions 3a, 3b, 17a, 17b, 31 Coil portions 5a, 5b, 20a, 20b, 34, 41 Coil conductors 6a, 6b, 21a, 21b, 35, 43 Magnetic layers 7, 22 36a, 36b, 42 Capacitance electrodes 8, 23, 37a, 37b Dielectric layer

Claims (10)

A ceramic electronic component comprising a coil part in which a coil conductor is embedded in a magnetic part and a capacitor part in which a capacitor electrode is embedded in a dielectric part,
The coil conductor and the capacitive electrode are formed of a conductive material mainly composed of Cu,
The magnetic part and the dielectric part are formed of a ferrite porcelain composition containing at least Fe, Mn, Zn, and Ni ,
The ferrite ceramic composition, the molar amount of Cu is 0 to 5 mol% in terms of CuO, and the molar content x mol% when converted to Fe in _Fe 2 _{O 3,} and Mn Mn ₂ When the content molar amount ymol% in terms of O ₃ is expressed by (x, y), (x, y) is A (25,1), B (47,1), C (47,7 .5), D (45, 7.5), E (45, 10), F (35, 10), G (35, 7.5), and H (25, 7.5) A ceramic electronic component characterized by being . The coil portion includes a plurality of magnetic layers constituting the magnetic portion and a plurality of coil pattern portions constituting the coil conductor, and the capacitor portion includes a plurality of portions constituting the dielectric portion. ceramic electronic component according to claim 1, wherein a plurality of electrode patterns portions constituting the capacitor electrode and the dielectric layer is characterized by being laminated alternately. The coil and the conductor and the capacitor electrode, a ceramic electronic component according to claim 1 or claim 2, wherein said magnetic body and said dielectric portion is characterized by comprising the simultaneous firing. A ceramic electronic component having a component body in which a coil conductor and a capacitive electrode are embedded in a magnetic part, and a capacitance is formed between the coil conductor and the capacitive electrode,
The coil conductor and the capacitive electrode are formed of a conductive material mainly composed of Cu,
The magnetic part is formed of a ferrite ceramic composition containing at least Fe, Mn, Zn, and Ni;
The ferrite ceramic composition, the molar amount of Cu is 0 to 5 mol% in terms of CuO, and the molar content x mol% when converted to Fe in _Fe 2 _{O 3,} and Mn Mn ₂ When the content molar amount ymol% in terms of O ₃ is expressed by (x, y), (x, y) is A (25,1), B (47,1), C (47,7 .5), D (45, 7.5), E (45, 10), F (35, 10), G (35, 7.5), and H (25, 7.5) ceramic electronic component, characterized in that. 5. The ceramic electronic component according to claim 4 , wherein the capacitor element includes the capacitor electrode sandwiched between the coil conductors. The ceramic electronic component according to claim 4 or 5, wherein the coil conductor and the capacitor electrode and the magnetic body portion are fired simultaneously. The ceramic electronic component according to any one of claims 1 to 6, wherein the ferrite porcelain composition has a Zn content molar amount of 6 mol% or more in terms of ZnO . 8. The ceramic electronic component according to claim 1, wherein the ferrite porcelain composition has a molar content of Zn of 33 mol% or less in terms of ZnO . 9. The ceramic electronic component according to any one of claims 1 to 8, characterized by comprising calcined at Cu-Cu 2 _O average oxygen content of under pressure or atmosphere. Containing Cu was 0 to 5 mol% molar amount in terms of CuO in and when the molar content x mol% when converted to Fe in _Fe 2 _{O 3,} and a Mn in terms of _Mn 2 _{O 3} When the molar amount ymol% is represented by (x, y), (x, y) is A (25, 1), B (47, 1), C (47, 7.5), D (45, 7.5), E (45, 10), F (35, 10), Fe (35, 7.5), and Fe compound and Mn compound so as to fill a region surrounded by H (25, 7.5) , Cu compound, Zn compound, and Ni compound are each weighed, and after mixing these weighed products, calcining step to produce calcined powder by calcining,
A ceramic thin layer production process for producing a ceramic thin layer from the calcined powder;
A conductive film forming step of forming a conductive film having a predetermined pattern mainly composed of Cu on the ceramic thin layer;
A laminated body forming step of laminating the ceramic thin-layer body on which the conductive film is formed in a predetermined order, and forming a laminated body;
A ceramic electronic comprising: a firing step of firing the laminate in a firing atmosphere of an equilibrium oxygen partial pressure of Cu-Cu ₂ O or less and simultaneously firing the ceramic thin-layer body and the conductive film. A manufacturing method for parts.

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