JP4796809B2 - Laminated electronic components - Google Patents

Description

  The present invention relates to a laminated electronic component. More specifically, the present invention relates to a multilayer electronic component having a structure in which a plurality of ceramic layers and a plurality of conductor layers are alternately stacked.

  In recent years, an increase in high-frequency noise has become a problem with the increase in the speed and density of integrated circuits and the increase in wiring length. This high frequency noise is caused by a decrease in power supply voltage due to so-called simultaneous switching. As a countermeasure, there is known a method of disposing a capacitor (decoupling capacitor) for the purpose of supplying power in the immediate vicinity of an integrated circuit. This capacitor is particularly required to be small, thin (short wiring length) and large capacity, and requires an extremely fine and highly accurate structure.

Conventionally, in the via conductor provided in the multilayer electronic component as described above, there are known problems of causing cracks in the outer peripheral edge of the via conductor and problems of poor connection between the via conductor and each internal electrode layer. The following Patent Documents 1 and 2 are known as methods for solving this problem. The following Patent Documents 1 and 2 are technologies using a conductive paste for via holes containing two types of conductive metal powders having different average particle diameters. It is.

JP 2004-273661 A JP 2004-228508 A

  In Patent Documents 1 and 2, when a via hole is formed by laser drilling, the connection failure between the internal conductor layer and the via conductor due to the unfired internal conductor layer retreating from the inner wall surface of the via hole is excellent. ing. However, it is difficult to prevent cracks that appear near the interface between the ceramic portion and the via conductor.

The present invention has been made to solve the above problems, the via conductor portion formed extending in the laminating direction of the laminated portion in which a plurality of ceramic layers and a plurality of conductor layers are alternately laminated, between the ceramic layer An object of the present invention is to provide a laminated electronic component using a via paste for laminated electronic components that can reliably prevent cracks.

That is, the present invention is as follows.
(1) a laminated portion in which a plurality of ceramic layers and a plurality of conductor layers are alternately laminated;
In a laminated electronic component comprising a via conductor portion that extends in the lamination direction of the laminated portion and is connected to a part of the conductor layer,
The via conductor portion has a conductive metal phase, and a ceramic base phase made of a ceramic base component that can be sintered with a ceramic component constituting the ceramic layer,
Co green body ceramic phase, Ri 10-45 vol% der in total the via conductor portion,
A bonding phase which is a common ceramic phase that is 10 μm or more inward into the via conductor portion in a cross section perpendicular to the laminating direction including the via conductor portion in the ceramic layer and is sintered with the ceramic layer. 5 or more locations
Having 5 or more conductive metal phases with a maximum length of 3.0 μm or more surrounded by the bonding phase,
Multilayer electronic component and the ceramic component and the co-matrix ceramic component constituting the ceramic layer has a same der Rukoto (hereinafter, simply referred to as "multilayer electronic component of the present invention").
( 2 ) a first via conductor portion extending in the laminating direction of the laminated portion and connected to every other conductor layer;
A second via conductor portion extending in the laminating direction of the laminated portion and connected to a conductor layer not connected to the first via conductor portion;
A first external terminal connected to an end of the first via conductor portion and led to the surface of the laminated portion;
The multilayer electronic component according to the above ( 1 ), which is a multilayer ceramic capacitor including a second external terminal connected to an end of the second via conductor portion and led to the surface of the multilayer portion.
( 3 ) The conductive metal component forming the conductive metal phase is nickel,
The multilayer electronic component according to (1) or (2), wherein the common substrate ceramic component is a titanate ceramic component.

According to the via paste for laminated electronic components, it is possible to reliably prevent cracks between the via conductor portion and the ceramic layer.
When the conductive metal powder contains large conductive metal particles having a particle size larger than the average particle size of the common ceramic powder, the cracks can be prevented more reliably.
When the large-diameter conductive metal particles are contained in an amount of 40% by volume or more of the entire conductive metal powder, the cracks can be prevented more reliably.
When the average particle size of the common substrate ceramic powder is larger than the average particle size of the ceramic powder contained in the unfired ceramic layer that becomes the ceramic layer, it is easy to match the timing of firing shrinkage between the via conductor portion and the ceramic layer. The crack between a conductor part and a ceramic layer can be prevented reliably.
According to the method for manufacturing a laminated electronic component , it is possible to reliably prevent cracks between the via conductor portion and the ceramic layer in the laminated electronic component.
According to the multilayer electronic component of the present invention in which the common ceramic phase is 10% by volume or more of the entire via conductor portion, cracks between the via conductor portion and the ceramic layer are surely prevented, and the reliability and durability are excellent. An electronic component is obtained.
According to another multilayer electronic component of the present invention having a ceramic substrate and a sintered ceramic phase that has entered into the via conductor inward direction and has a predetermined number or more, cracks between the via conductor and the ceramic layer are surely prevented. Thus, an electronic component having excellent reliability and durability can be obtained.
In the case of a multilayer ceramic capacitor including the first via conductor portion, the second via conductor portion, the first external terminal, and the second external terminal, cracks between the via conductor portion and the ceramic layer are reliably prevented, An electronic component having excellent reliability and durability can be obtained.

Hereinafter, the present invention will be described in detail.
[1] Via paste for multilayer electronic component (1) Conductive metal powder The via paste for multilayer component (hereinafter also simply referred to as “via paste”) contains a conductive metal powder and a common ceramic powder. The common substrate ceramic powder is characterized by containing 10% by volume or more of the total of the conductive metal powder and the common substrate ceramic powder.

  The above “conductive metal powder” includes metals such as nickel, copper, noble metals (gold, silver, platinum, palladium, rhodium, osmium, ruthenium and iridium), tin, zinc, cobalt, chromium, titanium, tantalum, tungsten and indium. (Conductive metal component) powder. Furthermore, the powder of the alloy which consists of 2 or more types of these metals is mentioned. Among these, nickel powder, nickel alloy (Ni—Cu, etc.) powder, surface-treated nickel powder, noble metal powder, and copper powder are preferable, and nickel powder and nickel alloy powder are more preferable. These conductive metal powders may be used alone or in combination of two or more.

The particle size distribution of the conductive metal powder is not particularly limited. That is, for example, the measured particle size distribution may be a powder having only one peak, or may be a powder having two or more peaks. The particle size distribution may be sharp or broad, but the cumulative mass with respect to the particle size (D ₉₀ ) at which the cumulative mass is ₉₀ % by mass of the total conductive metal powder is 10% of the total conductive metal powder. The ratio (D ₉₀ / D ₁₀ ) of the particle size (D ₁₀ ) to be mass% is 1.3 to 8.0 (more preferably 2.0 to 7.8, still more preferably 2.7 to 7.5). It is preferable that Within this range, the conductive metal phase and the common ceramic phase are more uniformly dispersed and can be reliably prevented from cracking between the via conductor portion and the ceramic layer.

Moreover, although an average particle diameter is not specifically limited, 0.2-3.5 micrometers is preferable, 0.5-3.0 micrometers is more preferable, 0.8-2.7 micrometers is still more preferable, 1.0-2.7 micrometers Is particularly preferred. When the average particle size is in this range, it is preferable that the aggregation of the conductive metal powder in the via paste can be more effectively suppressed, and particularly suitable for an electronic component that functions as a multilayer ceramic capacitor. The average particle size and particle size distribution can be measured by laser diffraction type particle size distribution measurement, but when this measurement is difficult, the methods of Examples described later can be used.
The content of the conductive metal powder is less than 90% by volume when the total amount with the later-described common substrate ceramic powder is 100% by volume.

Moreover, it is preferable that electroconductive metal powder contains the large-diameter electroconductive metal particle of a larger particle size than the average particle size of a sinter body ceramic powder.
The content of the large conductive metal particles is not particularly limited, but is 40% by volume or more of the conductive metal powder as a whole (preferably 40 to 100% by volume, more preferably 50 to 100% by volume, 75 to 100% by volume). It is preferable that

  The conductive metal powder may contain small-diameter conductive metal particles smaller than the average particle size of the common ceramic powder. Although content of this small diameter electroconductive metal particle is not specifically limited, It is preferable that it is 10-50 volume% (preferably 20-50 volume%) of the whole electroconductive metal powder.

(2) Sintered body ceramic powder The above-mentioned “sintered body ceramic powder” is a ceramic powder that can be sintered with a ceramic component constituting the ceramic layer. Examples of the ceramic component (community ceramic component) constituting the common ceramic powder include ceramic components having dielectric properties. That is, for example, titanate ceramic components (barium titanate, strontium titanate, calcium titanate, magnesium titanate), niobate ceramic components, tantalate ceramic components, titanium oxide, oxidation Examples include tungsten, alumina, zirconia, silica, magnesia, calcia, and the like. These ceramic components may contain only 1 type, and may contain 2 or more types. Further, when two or more kinds are contained, it may be a mixed component in which two or more kinds of ceramic components are mixed, or may be a composite component (composite oxide or the like) in which two or more kinds of ceramic components are compounded. Good.

  Furthermore, the glass component which has a dielectric characteristic is mentioned as said ceramic component. This glass usually contains at least Si, Al and O. Furthermore, as other elements, B, Ca, Mg, Sr, Ba, V, Cr, Mn, Co, Ni, Ga, Y, Zr, Nb, Mo, Tc, In, Sn, Ta, W, Re, Bi Each lanthanoid element and each actinoid element can be contained. These other elements may contain only 1 type and 2 or more types may contain.

  The ceramic component having the dielectric characteristics and the glass component having the dielectric characteristics may be used alone or in combination. Furthermore, the ceramic component constituting the ceramic layer of the multilayer electronic component and the ceramic component constituting the ceramic powder contained in the via paste may be the same or different, but the same composition system. Is preferred. That is, the common ceramic powder is preferably a ceramic powder composed of a ceramic component of the same composition system as the ceramic component constituting the ceramic layer of the multilayer electronic component.

  In addition, the same composition system means that the element types integrated up to over 70% by mass are the same when elements contained in the ceramic component are integrated in descending order of content (as oxide). However, the element species accumulated up to more than 40% by mass are the same, there are two or more other element types that are commonly contained, and the content of each of these two or more common element species When the difference is within 2N mass% between the two components (where N is the number of common element species), the same composition system is used. In addition, when the oxide conversion content of the element contained in one component is the same in two or more types, each element is included in the element type for judging the same composition system. The above oxide conversion is based on the most stable oxide in each element.

Moreover, the particle size distribution of the common substrate ceramic powder is not particularly limited. That is, for example, the measured particle size distribution may be a powder having only one peak, or may be a powder having two or more peaks. Further, the particle size distribution may be sharp or broad, but the particle size (D ₁₀ ) at which the cumulative mass is ₁₀ % by mass of the entire common ceramic powder, and the cumulative mass is the total of the common ceramic powder. The ratio to the particle size (D ₉₀ ) that is 10% by mass is preferably 1.3 to 7.0 (more preferably 3.5 to 4.4). Within this range, the conductive metal phase and the common ceramic phase are more uniformly dispersed and can be reliably prevented from cracking between the via conductor portion and the ceramic layer.

  The average particle size of the common ceramic powder is not particularly limited, but is preferably 0.3 to 2.0 μm, more preferably 0.3 to 1.8 μm, still more preferably 0.4 to 1.5 μm, and 5 to 1.3 μm is particularly preferable. When the average particle size is within this range, the conductive metal phase and the common ceramic phase are more uniformly dispersed and are preferable because cracks between the via conductor and the ceramic layer can be surely prevented. It is suitable for an electronic component that functions as a capacitor.

The average particle size of the common ceramic powder is preferably larger than the average particle size of the ceramic powder contained in the unfired ceramic layer that is fired to form the ceramic layer, and particularly 1.1 times or more. preferable. The average particle size of the common substrate ceramic powder is larger than the average particle size of the ceramic powder contained in the unfired ceramic layer, so that the timing of firing shrinkage between the via conductor portion and the ceramic layer can be easily adjusted. And the ceramic layer can be reliably prevented from cracking.
The average particle size and particle size distribution can be measured by laser diffraction type particle size distribution measurement, but when this measurement is difficult, the methods of Examples described later can be used.

The content of the co-matrix ceramic powder, more than 10% by volume of the total of the conductive metal powder and co-matrix ceramic powder (hereinafter usually 49% by volume) may be Re der, this content is 10 to 45 vol% There is preferably 12 to 40 vol%, more preferably 15 to 35% by volume. If it is this range, the said crack can be suppressed, ensuring the electroconductivity as a via conductor part enough.

  Further, the content of the conductive metal powder and the common ceramic powder with respect to the entire via paste is not particularly limited, but usually 30% by volume or more of the entire via paste (100% by volume) (preferably 40 to 70% by volume, more preferably Is 45 to 65 vol%, usually 70 vol% or less). If it is this range, it is easy to adjust to the optimal viscosity (for example, below 1,000,000 Pa * s as mentioned later) as a via paste, and is preferable. For example, when the total amount of via paste composed of inorganic powder (conductive metal powder and common substrate ceramic powder) and organic components (organic binder, solvent, plasticizer, antifoaming agent, etc. described later) is 100% by volume, inorganic The powder can be 30 volume% or more (preferably 40 to 70 volume%, more preferably 45 to 65 volume%, usually 70 volume% or less).

(4) Other components The via paste may contain other components in addition to the conductive metal powder and the common ceramic powder. Examples of other components include organic components. That is, for example, an organic binder, a solvent, a plasticizer, an antifoaming agent, etc. are mentioned.
Among these, organic binders include acrylic resins, celluloses such as alkyl cellulose (ethyl cellulose, methyl cellulose) and nitrocellulose, acrylic ester resins such as polymethyl methacrylate, butyral resins such as polyvinyl butyral, phenolic resins, and polyesters. Resin (alkyd resin, etc.). These may use only 1 type and may use 2 or more types together. Moreover, although content of an organic binder is not specifically limited, Usually, it is 10 volume% or less of the whole via paste.

  Solvents include ketone solvents (such as acetone and methyl ethyl ketone), hydrocarbon solvents (such as cyclohexane and toluene), monohydric alcohols (such as terpineol and butyl carbitol), and polyhydric alcohols (such as ethylene glycol and diethylene glycol). Etc. These solvents may be used alone or in combination of two or more. Although content of a solvent is not specifically limited, When the whole organic binder is 100 mass parts, it is preferable to contain in the ratio of 45-70 mass parts.

Furthermore, it is preferable to use an appropriate organic binder according to the type of organic binder to be used. Furthermore, it is preferable to contain a plasticizer in the ratio of 10-30 mass parts when the whole organic binder is 100 mass parts.
Moreover, it is preferable to contain an antifoamer in the ratio of 0.1-10 mass parts, when the whole via paste is 100 mass parts.

  The viscosity of the via paste is not particularly limited, but is preferably 1,000,000 Pa · s or less (more preferably 10,000 to 35,000 Pa · s, usually 5,000 Pa · s or more). If it is this range, a via hole can be reliably filled. The via hole diameter suitable for using this via paste is not particularly limited, but is preferably 50 to 200 μm (more preferably 50 to 150 μm). Furthermore, the aspect ratio of the via hole is not particularly limited, but is preferably 50 to 100 (more preferably 70 to 110).

  A laminated electronic component using via paste includes a laminated portion in which a plurality of ceramic layers and a plurality of conductor layers are alternately laminated, and a via conductor portion that extends in the lamination direction of the laminated portion and is connected to a part of the conductor layers. And comprising. Regarding the configuration of the multilayer electronic component, the configuration of the multilayer electronic component of the present invention described later can be applied as it is.

[2] Manufacturing method of laminated electronic component The manufacturing method of the laminated electronic component includes an unfired laminated portion forming step, a filling step, and a firing step.
The “unfired laminated portion forming step” is a step of obtaining an unfired laminated portion having a via hole that becomes a laminated portion.
The “unfired laminated portion” is an unfired body that is fired to form a laminated portion, and includes a via hole. This unsintered laminated part is a part in which unsintered ceramic layers to be the ceramic layers and unsintered conductor layers to be the conductor layers are alternately laminated.

  Although the structure of the said unbaking ceramic layer is not specifically limited, Usually, a ceramic powder is contained. The ceramic powder is preferably composed of a common ceramic powder contained in the via paste and a ceramic component that can be sintered. Moreover, it is preferable that the ceramic powder which comprises this unbaking ceramic layer is a thing with an average particle diameter smaller than the said common body ceramic powder. As the ceramic component constituting the ceramic powder, the ceramic component constituting the common ceramic powder can be applied as it is.

  Although the structure of the said unbaking conductor layer is not specifically limited, Usually, a conductive metal powder and an organic component are contained. Among these, as the conductive metal powder, the conductive metal powder contained in the via paste can be applied as it is. However, the conductive metal powder contained in the unfired conductor layer and the conductive metal powder contained in the via paste may be composed of the same component or different components. The conductive metal powder constituting the unfired conductor layer may have an average particle size smaller, larger or the same as the conductive metal powder constituting the via paste, but is small. It is preferable. As the organic component, the organic component can be applied as it is.

  The method for forming the unsintered laminated part is not particularly limited, and the unsintered ceramic layer with the unsintered conductor layer obtained by printing the unsintered conductor layer on the surface of the unsintered ceramic layer can be collectively laminated. . Further, the green ceramic layers and the green conductor layers can be alternately and sequentially stacked.

  The “via hole” may penetrate through the unfired laminate or may not penetrate therethrough. Moreover, the hole diameter (maximum length) of the via hole is not particularly limited, but may be 50 to 200 μm (more preferably 50 to 150 μm). Furthermore, the aspect ratio of the via hole is not particularly limited, but can be 50 to 100 (more preferably 70 to 110). The method for forming the via hole is not particularly limited, and the via hole can be formed using a laser beam, a drill, or the like.

  The “filling step” is a step of filling the via hole with the present via paste. The filling method in this filling step is not particularly limited, and for example, a screen printing method, a press-fitting printing method, or the like can be used.

  The “firing step” is a step of integrally firing the unfired laminated portion and the via paste filled in the via hole. The firing temperature, firing atmosphere, and the like in this firing step are not particularly limited, but usually the firing temperature is 1200 to 1350 ° C., and the firing atmosphere is an inert atmosphere or an oxidizing atmosphere. In particular, an inert atmosphere is used when the conductive metal powder contains Ni, Cu, or the like.

[3] Multilayer Electronic Component The multilayer electronic component of the present invention includes a multilayer portion and a via conductor portion, and the via conductor portion has a conductive metal phase and a common ceramic phase, and the common ceramic phase is a via conductor. total from 10 to 45 vol% der part is,
The cross section perpendicular to the stacking direction including the via conductor portion in the ceramic layer has at least 5 μm in the via conductor portion inward and has at least five joint phases that are sintered ceramic layers and sintered ceramic layers. And
Having 5 or more conductive metal phases with a maximum length of 3.0 μm or more surrounded by the bonding phase,
A ceramic component and a co-matrix ceramic component constituting the ceramic layer has a same der Rukoto.

  The “laminated portion” is a portion where a plurality of ceramic layers and a plurality of conductor layers are alternately laminated. “Alternately laminated” means that ceramic layers and conductor layers are alternately arranged in the laminating direction. That is, for example, as the structure of the stacked portion, the structure shown in FIG. In the structure of FIG. 1, it can be seen that the ceramic layers 111 and the conductor layers 112 are alternately laminated in order.

However, in this laminated portion, as a result, it is sufficient that the laminated layers are alternately laminated. For example, one or two or more unfired conductor layers are laminated for each of the unfired ceramic layers that are successively laminated. The structure obtained by firing the structure is also an alternately stacked structure according to the present invention.
The number of ceramic layers and conductor layers included in the laminate is not particularly limited, but is usually 2 or more (more preferably 10 or more, particularly 50 or more, usually 100 or more).

The “ceramic layer” is a layer that is disposed between conductor layers and functions as an insulating layer with respect to the conductor layers. In particular, the multilayer capacitor functions as a dielectric layer. The insulating properties and dielectric properties of the ceramic layer are not particularly limited, but usually have an insulating property of 10 ¹⁰ Ω · m or more. Further, the thickness of the ceramic layer is not particularly limited, but is usually 5.0 μm or less. However, these characteristics are preferably selected as appropriate according to the desired insulation, electrical characteristics such as capacitance and withstand voltage, and productivity, and further according to the production cost.

The ceramic component constituting the ceramic layer, Ru ceramic component der to be sintered and the ceramic component constituting the co-matrix ceramic layer. As the ceramic component constituting the ceramic layer, the ceramic component constituting the common ceramic layer can be applied as it is. A ceramic component constituting the ceramic layer, the ceramic component constituting the co-matrix ceramic layer may be the same, may be different, rather preferably be the same composition system as mentioned above This is the same in the present invention .

The “conductor layer” is a conductive layer. The conductivity is not particularly limited, but is usually 10 μΩ · cm or less. The conductor layer may be a patterned conductor layer having a predetermined shape such as a capacitor pattern or a circuit pattern, or may be an unpatterned conductor layer such as a ground. However, the various characteristics of the conductor layer are preferably selected as appropriate in accordance with electrical characteristics such as desired capacitance and withstand voltage, productivity, etc., and further in accordance with production costs.
The kind of the conductive metal component constituting the conductor layer is not particularly limited, and the component (conductive metal component) constituting the conductive metal powder can be applied as it is. However, the conductive metal component constituting the conductor layer and the conductive metal component constituting the via conductor portion (that is, the component constituting the conductive metal powder contained in the via paste) may be the same. , May be different.

The “via conductor portion” is a conductor portion extending in the stacking direction of the stacked portion and connected to a part of the conductor layer. In particular, in the multilayer capacitor, at least two adjacent layers of the ceramic layer and the conductor layer are disposed so as to penetrate in the lamination direction, and are connected to at least one of the penetrated conductor layers.
In general, at least one end of the via conductor portion is exposed or led out from the laminated portion. Therefore, the via conductor portion may be provided so as to penetrate the laminated portion, or may be provided in a state where only one end side penetrates and the other end side does not penetrate.

  The shape of the via conductor portion is not particularly limited, but is usually a columnar shape and further a columnar shape. This shape depends on the through hole. The size of the crotch and via conductors is not particularly limited and depends on the through hole. Usually, the maximum diameter (maximum length) can be 50 to 200 μm (more preferably 50 to 150 μm), and the aspect ratio Can be 50 to 150 (further 70 to 110).

Further, the via conductor portion has a conductive metal phase and a common ceramic phase. That is, for example, as shown in FIGS. 3 to 6 and FIGS. 9 to 12, the conductive metal phase 125 and the common ceramic phase 123 are provided.
The “conductive metal phase” is a conductive phase composed of a conductive metal component. As the conductive metal component, wherein the conductive metal powder can simply apply a conductive metal component constituting the, Ru nickel der in the present invention.

The “composite ceramic phase” is a phase composed of a ceramic component constituting the ceramic layer and a common ceramic component that can be sintered. As the common ceramic component, the common ceramic component constituting the common ceramic powder can be applied as it is.
The co-matrix ceramic phase, more than 10% by volume of the total via conductor portion (normally less than 49% by volume) may be Re der, the content is 10 to 45 vol%, preferably 12 to 40 vol%, 15 -35 volume% is more preferable.

The multilayer electronic component of the present invention includes a multilayer part and a via conductor part, the via conductor part has a conductive metal phase and a common ceramic phase, and includes a via conductor part in the ceramic layer of the multilayer part. The cross-section perpendicular to the inside of the via conductor part has an area of 10 μm or more inward and has 5 or more common ceramic phases (hereinafter simply referred to as “joining phases”) sintered with the ceramic layer.

  That is, as shown in FIGS. 3 to 5, a bonding phase in which the common ceramic phase and the ceramic layer are sintered is recognized on the outer peripheral portion of the via conductor portion. Among the bonding phases, at least 5 (more 10 or more, especially 15 or more) portions having a shape of 10 μm or more (10 μm or more toward the via center) in the via conductor portion in particular are provided. Further, a conductive metal phase having a maximum length of 3.0 μm or more surrounded by a continuous bonding phase from the ceramic layer (isolated from other conductive metal phases by being surrounded by a continuous bonding phase from the ceramic layer) The conductive metal phase (hereinafter referred to as “isolated conductive metal phase”) has 5 or more (more preferably 10 or more, especially 15 or more). These bonding phases are considered to be phases obtained by sintering the common ceramic powder contained in the via paste and the ceramic layer constituting the inner wall of the via hole. Since the ceramic layer and the via conductor portion have such a phase form, it is considered that cracks at the interface between the via conductor portion and the via hole are surely prevented in this multilayer electronic component. Furthermore, it is preferable that the common ceramic phase and the conductive metal phase are recognized in a well-balanced manner.

  Each of the “laminated part”, “ceramic layer”, and “conductor layer” in the laminated electronic component can be applied as it is. As the “via conductor portion”, the via conductor portion in the multilayer electronic component of the present invention can be applied as it is.

  The multilayer electronic component of the present invention is suitable as a multilayer capacitor, and is particularly suitable as a via array type multilayer ceramic capacitor. The structure of this multilayer capacitor is normally connected to the first via conductor portion extending in the laminating direction of the laminated portion and connected to every other conductor layer, and connected to the first via conductor portion extending in the laminating direction of the laminated portion. A second via conductor portion connected to a non-conductive layer, a first external terminal connected to an end portion of the first via conductor portion and led to the surface of the laminated portion, and an end portion of the second via conductor portion And a second external terminal led out to the surface of the laminated portion. The via array type multilayer ceramic capacitor has, for example, the structure of FIG. 1 in the embodiment.

  In the laminated electronic component of the present invention, other parts can be provided in addition to the laminated part and the via conductor part. An external terminal part is mentioned as another part. Of these, the external terminal part is usually a part to be plated, and when this part is provided, there should be no cracks on the inner wall of the via hole, the via conductor part and the interface as in the multilayer electronic component of the present invention. In particular, you can enjoy the superiority.

Hereinafter, the present invention will be specifically described by way of examples.
[1] Configuration of Multilayer Electronic Component FIG. 1 is a schematic cross-sectional view of a multilayer ceramic capacitor which is an example of the multilayer electronic component 1. The multilayer electronic component 1 is a via array type multilayer ceramic capacitor.
The multilayer electronic component 1 includes a multilayer part 11 in which a plurality of ceramic layers 111 and a plurality of conductor layers 112 are alternately laminated, and a via conductor that extends in the lamination direction of the multilayer part 11 and is connected to a part of the conductor layers 112. Part 12 (121 and 122).

  The ceramic layer 111 constituting the stacked portion 11 is made of barium titanate, and is disposed between the conductor layers 112 to function as a dielectric (insulator) of the conductor layer 112. The thickness of the ceramic layer 111 is about 5 μm. On the other hand, the conductor layer 112 is a layer having a thickness of 1.5 μm to 1.8 μm formed mainly of nickel.

  The via conductor portions 12 have a diameter of about 100 μm and an aspect ratio of about 90, and are arranged in a large number of lattices with a via pitch of about 400 μm. A part of the via conductor portions 12 extends in the stacking direction of the stacked portion 11. The first via conductor portion 121 is connected to every other conductor layer 121. The other portion of the via conductor portion 12 is a second via conductor portion 122 that is connected to the conductor layer 121 that extends in the stacking direction of the stacked portion 11 and is not connected to the first via conductor portion 121. These via conductor portions 12 are formed using nickel as a conductive metal component and barium titanate as a common ceramic component.

  The first via conductor portion 121 and the second via conductor portion 122 are not connected to a common conductor layer. In addition, a clearance hole having a diameter of about 300 μm is formed in the conductor layer 121 connected to the first via conductor portion, and a second conductor portion having a diameter of about 100 μm passes through the clearance hole of the conductor layer 121, The conductor layer 121 is insulated.

  Further, the first external terminal 131 connected to the end portion of the first via conductor portion 121 and led to the surface of the multilayer portion 11 and the end portion of the second via conductor portion 122 are connected to the surface of the multilayer portion 11. A second external terminal 132 that is led out.

  Further, one surface side of the laminated portion 11 is connected to the first external terminal 131 (solder bump) and the second external terminal 132 (solder bump) arranged on the one surface side, so that another electronic component 2 (semiconductor integrated circuit element) is connected. It can be connected to the mounting board). On the other hand, the other surface side of the laminated portion 11 is connected to the first external terminal 131 (solder bump) and the second external terminal 132 (solder bump) arranged on the other surface side, so that another electronic component 3 (mother board) is connected. ) And can be connected. The first external terminal 131 and the second external terminal are each formed mainly of nickel, and the surfaces thereof are covered with a nickel plating layer and a gold plating layer.

[2] Manufacture of laminated electronic components (1) Unfired laminated part forming step (1-1) Formation of unfired ceramic layer A slurry for an unfired ceramic layer containing barium titanate powder is applied on a carrier film and dried. Thus, an unfired ceramic green sheet disposed on the carrier film so as to be peeled was obtained. The green ceramic green sheet is then cut into a desired shape to form a green ceramic layer.

(1-2) Formation of Unsintered Conductor Portion A screen mask is disposed on the unsintered ceramic green sheet obtained in (1-1) above, and the conductor layer paste is printed by screen printing and dried. An unfired conductor layer having a thickness of 2 to 3 μm was formed.

(1-3) Multilayer pressure bonding of unsintered ceramic layer and unsintered conductor layer 100 to 120 green sheets on which the unsintered conductor layer obtained in (1-2) above is laminated, Lamination was performed so that the fired conductor layers were alternately arranged. Furthermore, the unfired cover part obtained by laminating only three layers of unfired ceramic green sheets is arranged on the front and back of the laminate, and the unfired cover parts, unfired ceramic layers and unfired conductor layers are alternately arranged. It was set as the order of the laminated part and the unbaked cover part which were made. Then, at a temperature 60 ° C. to 80 ° C. in the stacking direction by using the laminating apparatus, to obtain a green laminate having a thickness of about 1mm by pressing under the conditions of pressing force ^{300kg / cm 2 ~1000kg / cm 2} .

(1-4) Formation of via hole A via hole having a diameter of about 120 μm was regularly drilled in the green laminate obtained in (1-3) above using a laser processing machine.

(2) Filling process Via paste is press-fitted into the via hole formed in (1-4) above at a pressure of 2.0 MPa to 7.5 MPa using a paste press-fitting device to form an unfired via conductor portion. did.

(3) Formation of unsintered external terminals Thickness disposed on one surface of the unsintered laminate on one end side of the unsintered via conductor obtained in (2) above (the side on which the other electronic component 2 can be connected) The external terminal paste was printed and applied through a metal mask of about 30 μm and dried to form an unfired external conductor.
Next, the external terminal paste is printed on the other end side of the unfired via conductor (the side on which the other electronic component 3 can be connected) through a screen mask having a thickness of about 25 μm disposed on the other surface of the unfired laminate. It was applied and dried to form an unfired outer conductor.

(4) Firing step After breaking grooves were put in a lattice shape in the unfired laminate obtained up to (3) above, the unfired laminate was degreased and then fired.

(5) Formation of plating layer covering external terminals Electroless nickel plating is applied to the surface of the first external terminal 131 and the second external terminal 132 of the sintered body obtained in the above (4) to a thickness of about 0.5 μm to It formed in 3.0 micrometers. Thereafter, a plating layer having a thickness of about 0.1 μm to 1.0 μm was further formed by electrolytic gold plating. By plating the surface of the external terminal, the common ceramic phase contained in the external terminal can be prevented from being exposed to the terminal surface, and the wettability of the terminal portion can be improved.

(6) Cutting of sintered body The sintered body was broken along the break grooves formed in the above (4) to obtain a plurality of laminated electronic components 11.

[3] Evaluation Using Various Pastes In the manufacturing method of [2], the following slurry and paste are used as the unfired ceramic layer slurry and conductor layer paste, respectively, and the following via pastes A to D are used as via pastes. The obtained via conductor part was evaluated.

(1) Slurry for unsintered ceramic layer When the entire slurry for unsintered ceramic layer is 100% by mass, it contains 60% by mass ceramic powder and 40% by mass organic component, and has a viscosity of 0.5 Pa · s. It is.
The ceramic powder is mainly composed of barium titanate and has an average particle diameter (D50) of 0.6 μm (D10 = 0.3 μm, D90 = 1.0 μm).

(2) Conductor layer paste When the total conductor layer paste is 100% by mass, it contains 55% by mass of inorganic powder and 45% by mass of an organic component, and has a viscosity of 20 Pa · s.
The said inorganic powder consists of a common body ceramic powder and nickel powder, and when these are made into 100 volume%, a common body ceramic powder contains 15 volume% and nickel powder 85 volume%.
The above-mentioned common substrate ceramic powder is barium titanate having a purity of 99% or more and has an average particle diameter (D50) of 0.1 μm.
The nickel powder is a nickel powder having a purity of 99% or more and an average particle diameter (D50) of 0.4 μm.

(3) Via paste A (Example 1)
90% by mass of inorganic powder and 10% by mass of organic components when the entire via paste is 100% by mass (55% by volume of inorganic powder and 45% by volume of organic when the total via paste is 100% by volume) Component), and measured with a viscosity of 20,000 Pa · s {rotary cylindrical viscometer (RB-80U, manufactured by Toki Sangyo Co., Ltd.) under the conditions of a rotational speed of the rotor of 1 rpm and a temperature of 25 ° C. The same shall apply hereinafter.
The inorganic powder is composed of a common ceramic powder and a nickel powder. When the total of these is 100% by volume, the common ceramic powder contains 20% by volume and 80% by volume of the nickel powder.
The above-mentioned common substrate ceramic powder is barium titanate and has an average particle diameter (D50) of 0.64 μm (D10 = 0.29 μm, D90 = 1.15 μm).
The nickel powder is a nickel powder having a purity of 99% or more and has an average particle diameter (D50) of 2.4 μm (D10 = 0.5 μm, D90 = 3.5 μm). Furthermore, the large-diameter conductive metal powder is 90% by volume of the entire nickel powder.
The organic component contains an organic binder (ethyl cellulose) 4.5 mass% (content with respect to the entire via paste), an organic solvent (terpineol), a dispersant and an antioxidant.

(4) Via paste B (Example 2)
90% by mass of inorganic powder and 10% by mass of organic component when the entire via paste is 100% by mass (50% by volume of inorganic powder and 50% by volume of organic when the entire via paste is 100% by volume) Component) and a viscosity of 30,000 Pa · s.
The inorganic powder is composed of a common ceramic powder and a nickel powder, and when the total of these is 100% by volume, the common ceramic powder contains 30% by volume and 70% by volume of the nickel powder.
The above-mentioned common base ceramic powder is barium titanate and has an average particle diameter (D50) of 1.12 μm (D10 = 0.65 μm, D90 = 1.57 μm).
The nickel powder is a nickel powder having a purity of 99% or more, and has an average particle diameter (D50) of 1.5 μm (D10 = 0.8 μm, D90 = 2.0 μm). Furthermore, the large-diameter conductive metal powder is 75% by volume of the entire nickel powder.
The organic component is common to the via paste A of Example 1.

(5) Via paste C (Comparative Example 1)
90% by mass of inorganic powder and 10% by mass of organic components when the entire via paste is 100% by mass (55% by volume of inorganic powder and 45% by volume of organic when the total via paste is 100% by volume) Component) and a viscosity of 30,000 Pa · s.
The inorganic powder is composed of a common ceramic powder and a nickel powder. When the total is 100% by volume, the common ceramic powder contains 7.5% by volume and 82.5% by volume of nickel powder. The
The above-mentioned common substrate ceramic powder is barium titanate and has an average particle diameter (D50) of 0.64 μm (D10 = 0.29 μm, D90 = 1.15 μm).
The nickel powder is a nickel powder having a purity of 99% or more and has an average particle diameter (D50) of 2.0 μm (D10 = 0.5 μm, D90 = 2.5 μm). Furthermore, the large-diameter conductive metal powder is 80% by volume of the entire nickel powder.
The organic component is common to the via paste A of Example 1.

(6) Via paste D (Comparative Example 2)
90% by mass of inorganic powder and 10% by mass of organic components when the entire via paste is 100% by mass (55% by volume of inorganic powder and 45% by volume of organic when the total via paste is 100% by volume) Component) and a viscosity of 20,000 Pa · s.
The inorganic powder is composed of a common ceramic powder and a nickel powder. When the total of these is 100% by volume, the common ceramic powder contains 2% by volume and 98% by volume of the nickel powder.
The above-mentioned common substrate ceramic powder is barium titanate and has an average particle diameter (D50) of 0.64 μm (D10 = 0.29 μm, D90 = 1.15 μm).
The nickel powder is a nickel powder having a purity of 99% or more and has an average particle diameter (D50) of 0.3 μm (D10 = 0.1 μm, D90 = 0.6 μm). Furthermore, the large-diameter conductive metal powder is 5% by volume of the entire nickel powder.
The organic component is common to the via paste A of Example 1.

(7) Results of Example A cross section perpendicular to the stacking direction including the via conductor portion in the ceramic layer of the multilayer electronic component including the via conductor portion obtained by using the via paste A (Example 1) is an electron. FIG. 2 shows an image obtained by enlarging about 700 times using a microscope. Further, FIG. 3 is an image obtained by dividing FIG. 2 into four parts in the vertical direction and further enlarging each part. The cross section is a via conductor portion in the cover portion 111 ′ (actually sintered and integrated) on the side where the other electronic component 2 is arranged in the laminated electronic component in FIG. It is a cross section.
Similarly, the image by the multilayer electronic component obtained using the via paste B (Example 2) is shown in FIG.
Similarly, FIG. 8 shows an image of a laminated electronic component obtained by using via paste C (Comparative Example 1), and FIG. 8 is an image obtained by further dividing FIG. It was shown to.
Similarly, the image by the laminated electronic component obtained using the via paste D (Comparative Example 2) is shown in FIG.

(8) Effect of Example In FIGS. 8 to 13 obtained using the via paste of the comparative example, cracks are recognized in the outer peripheral portion of the via conductor portion. Although the conductive metal phase 125 and the common ceramic phase 123 are recognized in the via conductor portion, the proportion of the common ceramic phase is about 7.5% in terms of area (that is, about 7.5% in terms of volume). small. Further, it can be seen that the ceramic layer and the bonding phase 124 are hardly recognized, and that the bonding phase is small.
Further, in FIGS. 8 to 13, it can be seen that pores are hardly recognized in the common substrate portion of the via conductor portion, and the area ratio is 1%.

  In contrast, no cracks are observed in FIGS. 2 to 7 obtained using the via paste of the example. 2-7, the conductive metal phase 125 and the common ceramic phase 123 are recognized in the via conductor, and the proportion of the common ceramic phase is about 30% in terms of area (that is, about 30 in terms of volume). %) And large. Furthermore, it can be seen that these phases are arranged in a balanced manner.

  Moreover, in FIGS. 2-7, the ceramic layer and the sintered joining phase 124 which comprise a laminated body are recognized over the perimeter of the outer peripheral part of the via conductor part of a common substrate ceramic layer. Furthermore, 15 or more portions of the bonding phase entering 10 μm or more inward in the via conductor portion are recognized in FIG. 2 and 10 or more portions in FIG. In particular, 7 or more isolated conductive metal phases having a maximum length of 3 μm or more are observed in FIG. 2 and 5 or more in FIG.

Moreover, in FIGS. 2-7, many pores with a diameter of 5 micrometers or less are recognized by the common base ceramic part of a via conductor part, and it is 5% of the whole via conductor part by area ratio. It can also be seen that the pores are arranged in the via conductor portion in the same balance as the ceramic layer.
This is a different part from FIGS. When using the via paste of the comparative example, the firing shrinkage cannot be adjusted sufficiently between the via paste and the unfired ceramic layer, and the shrinkage starts from the via paste too early or shrinks too quickly. This is probably because of this. That is, it is conceivable that pores are pushed out from the via conductor portion and appear as cracks at the interface with the ceramic layer.
On the other hand, when the via paste of the example is used, it is considered that the firing shrinkage starts at substantially the same timing as the ceramic layer or the shrinkage behavior is approximate. That is, no gap is formed as a crack, and a gap is formed as a pore inside the via conductor.

  In addition, in this invention, it can restrict to what is shown to said specific Example, It can be set as the Example variously changed within the range of this invention according to the objective and the use.

  The present invention is widely used in the field of electronic components. As this multilayer electronic component, a capacitor (particularly via array capacitor), a wiring board, an interposer, a multilayer ceramic part integrally including a capacitor in a ceramic substrate, a multilayer including a capacitor and / or a resonator and an inductor integrally. It includes at least one of substrates such as ceramic parts, general-purpose boards, functional boards (such as LTCC multilayer devices) in which various functional parts are embedded, packages such as MPU and SAW, individual parts, boards and packages. Examples include modules.

It is explanatory drawing which shows typically the cross section of an example of the multilayer electronic component of this invention. FIG. 3 is an explanatory diagram showing an enlarged cross section of a via conductor portion using the via paste A of Example 1. It is explanatory drawing which expands and shows further the upper right 1/4 part of FIG. It is explanatory drawing which expands further and shows the lower right 1/4 part of FIG. It is explanatory drawing which expands further and shows the upper left 1/4 part of FIG. It is explanatory drawing which expands further and shows the lower left 1/4 part of FIG. It is explanatory drawing which expands and shows the cross section of the via conductor part using the via paste B of Example 2. FIG. It is explanatory drawing which expands and shows the cross section of the via conductor part using the via paste C of the comparative example 1. FIG. It is explanatory drawing which expands and shows further the upper right 1/4 part of FIG. It is explanatory drawing which expands further and shows the lower right 1/4 part of FIG. It is explanatory drawing which expands further and shows the upper left 1/4 part of FIG. It is explanatory drawing which expands further and shows the lower left 1/4 part of FIG. It is explanatory drawing which expands and shows the cross section of the via conductor part using the via paste D of the comparative example 2. FIG.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1; Multilayer electronic component (via array type multilayer ceramic capacitor), 11; Laminate part, 111; Ceramic layer, 111 '; Cover part, 112; Conductor layer, 113; Via hole, 12: Via conductor part, 121; Portion, 122; second via conductor portion, 131; first external terminal, 132; second external terminal, 123; common ceramic phase, 124; bonding phase, 125; conductive metal phase, 125 '; Phase 126; pore 127; crack 2; other electronic component 3; further other electronic component.

Claims (3)

A laminated portion in which a plurality of ceramic layers and a plurality of conductor layers are alternately laminated;
In a laminated electronic component comprising a via conductor portion that extends in the lamination direction of the laminated portion and is connected to a part of the conductor layer,
The via conductor portion has a conductive metal phase, and a ceramic base phase made of a ceramic base component that can be sintered with a ceramic component constituting the ceramic layer,
Co green body ceramic phase, Ri 10-45 vol% der in total the via conductor portion,
A bonding phase which is a common ceramic phase that is 10 μm or more inward into the via conductor portion in a cross section perpendicular to the laminating direction including the via conductor portion in the ceramic layer and is sintered with the ceramic layer. 5 or more locations
Having 5 or more conductive metal phases with a maximum length of 3.0 μm or more surrounded by the bonding phase,
Multilayer electronic component and the ceramic component and the co-matrix ceramic component constituting the ceramic layer has a same der Rukoto. A first via conductor portion extending in the laminating direction of the laminated portion and connected to every other conductor layer;
A second via conductor portion extending in the laminating direction of the laminated portion and connected to a conductor layer not connected to the first via conductor portion;
A first external terminal connected to an end of the first via conductor portion and led to the surface of the laminated portion;
2. The multilayer electronic component according to claim 1 , wherein the multilayer electronic capacitor includes a second external terminal connected to an end portion of the second via conductor portion and led to a surface of the multilayer portion. The conductive metal component forming the conductive metal phase is nickel,
The multilayer electronic component according to claim 1, wherein the common substrate ceramic component is a titanate ceramic component.