Patent Application
20100038013
1. Field of the Invention
The present invention relates to a method for manufacturing a multilayer ceramic electronic device, and in particular, the present invention relates to a method for manufacturing a multilayer ceramic electronic device using a so-called non-shrinkage process.
2. Description of the Related Art
A multilayer ceramic substrate as one example of a multilayer ceramic electronic device has a plurality of laminated ceramic layers, and in general, conductive patterns are formed on surfaces and inside the ceramic layers. As the conductive patterns described above, for example, in-plane conductors extending in a plane direction of the ceramic layers and interlayer connection conductors (represented by via hole conductors) extending to penetrate the ceramic layers in a thickness direction may be mentioned.
In general, the multilayer ceramic substrate as described above mounts surface mount electronic devices, such as a semiconductor device and a chip multilayer capacitor, and electrically connects between these surface-mount electronic devices. In addition, in the case in which passive elements, such as a capacitor and an inductor, are embedded in the multilayer ceramic substrate, the passive elements are formed from the in-plane conductors and interlayer connection conductors and are, whenever necessary, connected with the individual surface mount electronic devices.
In order to form a multilayer ceramic substrate having more multi-functions, higher functions, and more superior performance, the conductive patterns described above must be formed to have a high accuracy and a high density.
Incidentally, in order to obtain a multilayer ceramic substrate, an unsintered ceramic laminate formed of laminated ceramic green sheets which are to be formed into ceramic layers must be fired. In this firing step, the ceramic green sheets are shrunk due to the loss of a binder contained therein and/or sintering of a ceramic powder, and in particular in the case of a multilayer ceramic substrate having a large area, the shrinkage is not likely to uniformly occur over the entire substrate. Hence, dimensional errors may be generated in a plane direction of the multilayer ceramic substrate due to non-uniform shrinkage, and/or the entire multilayer ceramic substrate may be warped or undulated in some cases.
As a result, the conductive patterns may be undesirably deformed and/or warped, and in more particular, the positional accuracy of the in-plane conductors and that of the interlayer connection conductors may be degraded, or disconnection may occur in the in-plane conductors and the interlayer connection conductors in some cases. The deformation and the warping generated in the conductive patterns are primary causes of preventing an increase in density of the conductive pattern.
Accordingly, for example, in Japanese Patent No. 2554415, a technique which uses a so-called non-shrinkage process, has been proposed in which when a multilayer ceramic substrate is manufactured, a firing shrinkage thereof in a plane direction is substantially inhibited.
In this non-shrinkage process, base-layer ceramic green sheets are prepared which are primarily composed of a base-layer ceramic powder formed by mixing a ceramic powder such as Al2O3 and a glass powder such as a borosilicate glass, and in addition, restriction-layer ceramic green sheets primarily composed of an Al2O3 powder, for example, are prepared. Subsequently, after in-plane conductors and interlayer connection conductors are formed on and in the base-layer ceramic green sheets, these ceramic green sheets are laminated to each other to form an unsintered ceramic laminate, and the restriction-layer ceramic green sheets are disposed on the top and the bottom primary surfaces of this unsintered ceramic laminate and are then pressure-bonded thereto, so that a composite laminate composed of the unsintered ceramic laminate and the restriction layers provided thereon is formed.
The composite laminate thus obtained is processed by a heat treatment to remove organic components, such as a binder, contained in the individual ceramic green sheets and is then fired at a temperature at which the unsintered ceramic laminate is sintered, that is, at a temperature at which the base-layer ceramic powder is sintered. In this firing step, since the Al2O3 powder contained in the restriction layers is not substantially sintered, the restriction layers are not substantially shrunk, so that a restriction force works on each of the top and the bottom primary surfaces of the unsintered ceramic laminate. As a result, the shrinkage of the unsintered ceramic laminate in a plane direction is substantially suppressed, and the unsintered ceramic laminate is shrunk substantially only in a thickness direction. In addition, after the firing step, when pore layers composed of the Al2O3 powder derived from the restriction layers are removed, a sintered ceramic laminate, which is the multilayer ceramic substrate, is obtained.
According to the non-shrinkage process described above, since the dimensional accuracy of the laminated base-layer ceramic green sheets is maintained in a plane direction, uneven deformation is not likely to occur, and thereby undesired deformation and warping of the conductive patterns are not likely to occur, so that a multilayer ceramic substrate having a highly reliable conductive patterns which are formed with high accuracy can be obtained.
However, as for the properties of the restriction layer of the non-shrinkage process, the following problems occur.
That is, according to the non-shrinkage process, since the restriction layer strongly restricts the primary surface of the unsintered ceramic laminate, the shrinkage of the unsintered ceramic laminate is suppressed, and hence the multilayer ceramic substrate can be formed with high accuracy. On the other hand, as the restriction force generated by the restriction layer is increased, the restriction layer becomes difficult to be removed after a firing step. Hence, the restriction layer may partly remain to adhere, for example, to a conductor provided on a surface of the multilayer ceramic substrate in some cases, and in this case, plating properties and/or wire bonding properties to this conductor are degraded. In order to solve this problem, although a powerful cleaning apparatus has been proposed, damage to the substrate surface is serious, and the cost is inevitably increased.
For example, when the particle diameter of an inorganic powder, such as an Al2O3 powder, used for the restriction layer is decreased, since the glass in the base layer and the inorganic powder particles in the restriction layer are likely to react with each other at an interface between the base layer and the restriction layer, a reaction product is easily generated at the interface, and hence a strong bond state can be formed between the base layer and the restriction layer. However, this strong bond state conversely causes a problem in that the restriction layer and also the reaction product become difficult to be removed.
On the other hand, when the particle diameter of the inorganic powder in the restriction layer is increased, since the glass in the base layer and the inorganic powder particles in the restriction layer are not likely to react with each other, the restriction layer can be easily removed. However, a force suppressing the shrinkage in a plane direction generated by the restriction layer is decreased, and in some cases, the shrinkage may not be suppressed.
As described above, although the adjustment of the particle diameter of the inorganic powder in the restriction layer is important, it is very difficult to simultaneously satisfy high restriction performance of the restriction layer and easy removal thereof, and thereby the non-shrinkage process has not been satisfactorily carried out.
In view of the above problems, preferred embodiments of the present invention provide a method for manufacturing a multilayer ceramic electronic device, such as a multilayer ceramic substrate.
According to a preferred embodiment of the present invention, a method for manufacturing a multilayer ceramic substrate includes a first step of forming an unsintered ceramic laminate containing a low-temperature sinterable ceramic powder; a second step of disposing a restriction layer containing a sintering resistant ceramic powder which is not substantially sintered at a temperature at which the low-temperature sinterable ceramic powder is sintered on at least one primary surface of the unsintered ceramic laminate; a third step of firing the unsintered ceramic laminate on which the restriction layer is disposed at a temperature at which the low-temperature sinterable ceramic powder is sintered so as to obtain a multilayer ceramic electronic device; and a subsequent fourth step of removing the restriction layer from the multilayer ceramic electronic device.
In order to solve the technical problems described above, the method for manufacturing a multilayer ceramic substrate described above includes the following steps.
First, the unsintered ceramic laminate formed in the first step includes a first base layer which has a first conductive pattern containing Ag as a primary component and which contains a first low-temperature sinterable ceramic powder, and a second base layer which has a second conductive pattern containing Ag as a primary component and which contains a second low-temperature sinterable ceramic powder. In this case, the second base layer is formed to have a composition so that the Ag is likely to diffuse during firing as compared to that of the first base layer. In addition, the second base layer is disposed along at least one primary surface of the unsintered ceramic laminate. In the second step, the restriction layer is disposed so as to be in contact with the second base layer of the unsintered ceramic laminate.
In the unsintered ceramic laminate described above, the first and the second low-temperature sinterable ceramic powders preferably include the same constituent elements. In this case, the first and the second low-temperature sinterable ceramic powders preferably contain a first and a second glass powder, respectively, and since the second base layer is, in the first step, caused to have a composition so that Ag is likely to diffuse as compared to that of the first base layer, a composition ratio of a glass forming the first glass powder and that of a glass forming the second glass powder are made different from each other.
The method for manufacturing a multilayer ceramic electronic device according to a preferred embodiment of the present invention may further include, after the fourth step is performed, a step of mounting a surface mount electronic device on the multilayer ceramic electronic device.
According to various preferred embodiments of the present invention, since the second layer in contact with the restriction layer has a composition so that Ag is likely to diffuse, the glass softening point thereof decreases, and hence a strong bond state with the restriction layer can be obtained. As a result, a restriction force generated by the restriction layer can be improved, and a sufficient restriction force can be applied to the unsintered ceramic laminate in the third step, so that the multilayer ceramic electronic device can be manufactured with high accuracy.
In addition, as described above, since a high restriction force can be obtained by the restriction layer, as the sintering resistant ceramic powder contained in the restriction layer, a ceramic powder having a relatively large particle diameter can be used. Hence, in the fourth step, a state in which the restriction layer can be easily removed can be realized without causing any problems.
In addition, since the second base layer in which Ag is likely to diffuse may be disposed only at a position in contact with the restriction layer, Ag does not easily diffuse in the entire multilayer ceramic electronic device. Accordingly, degradation in electrical properties, such as degradation in insulating reliability, caused by Ag diffusion can be suppressed to a minimum level.
In the unsintered ceramic laminate described above, when the first low-temperature sinterable ceramic powder and the second low-temperature sinterable ceramic powder contain the same constituent elements, since an intermediate product is not formed between the first base layer and the second base layer in the firing, a bonding force between the first base layer and the second base layer can be increased.
In the case described above, when the first and the second low-temperature sinterable ceramic powders contain the first and the second glass powder, respectively, since the second base layer is formed in the first step to have a composition so that Ag is likely to diffuse as compared to that of the first base layer, Ag diffusivity can be easily controlled when the composition ratio of the glass forming the first glass powder and that of the glass forming the second glass powder can be easily made different from each other.
Other features, elements, steps, characteristics and advantages of the present invention will become more apparent from the following detailed description of preferred embodiments of the present invention with reference to the attached drawings.
First, as shown in
The first and the second low-temperature sinterable ceramic powders preferably contain the same constituent elements. More particularly, for example, after a mixture including 5 to 20 parts by weight of B2O3 to 100 parts by weight of a powder which contains 0 to 55 percent by weight of CaO, 45 to 70 percent by weight of SiO2, 0 to 30 percent by weight of Al2O3, and 0 to 10 percent by weight of impurities is vitrified by melting at a temperature of 1,200° C. or more, followed by performing quenching in water and pulverizing, so that a CaO—SiO2—Al2O3—B2O3-based glass powder having an average particle diameter of 3.0 to 3.5 μm is formed. This glass powder is mixed with an alumina powder, and the mixtures thus obtained are used as the first and the second low-temperature sinterable ceramic powders.
In addition, in order to easily cause diffusion of Ag in the second base layer 2 as compared to that in the first base layer 1, for example, the composition ratio of a glass forming the glass powder is adjusted. That is, the composition ratio of a first glass powder contained in the first low-temperature sinterable ceramic powder is made different from that of a second glass powder contained in the second low-temperature sinterable ceramic powder. As one example, in the CaO—SiO2—Al2O3—B2O3-based glass powder, when the amount of B2O3 is increased, the softening point of the glass decreases, and Ag diffusion is likely to occur; hence, the amount of B2O3 of the glass forming the second glass powder is preferably larger than that of the glass forming the first glass powder.
As the binder described above, for example, an acrylic or a butyral-based resin may preferably be used; as the solvent, for example, toluene, xylene, or a water-based solvent may preferably be used; and as the plasticizer, for example, DOP (dioctyl phthalate) or DBP (dibutyl phthalate) may preferably be used.
In addition, although the unsintered first and second base layers 1 and 2 are preferably provided using the green sheets 1a and 2a, respectively, formed by the casting method described above, they may also be provided using unsintered thick-film printing layers formed by a thick film printing method.
Next, again with reference to
In addition, a conductive paste is printed on the base-layer green sheets 1a and 2a, so that unsintered in-plane conductors 7 and 8 are respectively formed. In the preferred embodiments shown in the figures, in-plane conductors 9 are also formed on a restriction-layer green sheet 11a which will be described later.
As the conductive paste forming the above interlayer connection conductors 5 and 6 and the in-plane conductors 7 to 9, a paste primarily composed of Ag is preferably used, for example.
In addition, also as shown in
The restriction-layer green sheets 10a and 11a are formed in such a way that the sintering resistant ceramic powder is dispersed in a vehicle composed of a binder, a solvent, a plasticizer, and the like to form a slurry, and the slurry thus obtained is formed into sheets by a casting method, such as a doctor blade method.
Next, the first base-layer green sheets 1a and the second base-layer green sheets 2a, which are provided with the conductive patterns, such as the interlayer connection conductors 5 and 6 and the in-plane conductors 7 to 9, are laminated to each other, so that an unsintered ceramic laminate 12 as shown in
In addition, the restriction-layer green sheets 10a and 11a are laminated so as to sandwich the unsintered ceramic laminate 12 in a lamination direction, so that the restriction layers 10 and 11 are provided. In this lamination state, the restriction layers 10 and 11 are in contact with the second base layers 2. In addition, instead of providing the restriction layers 10 and 11 using the green sheets 10a and 11a, they may be provided using thick-film printing layers formed by a thick film printing method.
The unsintered ceramic laminate 12 thus obtained which is provided with the restriction layers 10 and 11 is pressed by an isostatic press or a uniaxial press using a mold, so that a composite laminate 13 is obtained.
When the unsintered ceramic laminate 12 shown in
Next, the composite laminate 13 is fired at a temperature, for example, of 1,050° C. or less and more preferably 800 to 1,000° C. at which the first and the second low-temperature sinterable ceramic powders contained in the first and the second base layers 1 and 2, respectively, are sintered.
As a result of the above firing step, in the composite laminate 13, the restriction layers 10 and 11 are not substantially sintered, but the unsintered ceramic laminate 12 is sintered, so that as shown in
As apparent when
In addition, as described above, in the unsintered ceramic laminate 12, the first low-temperature sinterable ceramic powder contained in the first base layer 1 and the second low-temperature sinterable ceramic powder contained in the second base layer 2 contain the same constituent elements. Accordingly, in the firing described above, since an intermediate product is not formed between the first base layer 1 and the second base layer 2, the bonding force between the first base layer 1 and the second base layer 2 can be increased, so that generation of peeling therebetween can be prevented.
In addition, a thickness T1 of the unsintered ceramic laminate 12 of
Next, the restriction layers 10 and 11 are removed from the fired composited laminate 13 by a method, such as wet blast, sand blast, or brushing, so that the multilayer ceramic substrate 14 as shown in
Next, whenever necessary, the surfaces of the multilayer ceramic substrate 14 are cleaned. In this step, an excessively strong cleaning force is not necessarily applied. As a cleaning method, a physical treatment, such as ultrasonic cleaning or blasting of alumina abrasive particles or the like, and a chemical treatment, such as etching, may be used alone or in combination.
Subsequently, plating is performed on some of the in-plane conductors 7 to 9 which are exposed at the surfaces of the multilayer ceramic substrate 14. This plating is performed to enhance mounting reliability of surface mount electronic devices which will be described later, and for example, plating of Ni/Au, Ni/Pd/Au, Ni/Sn, or the like is performed. As a plating method, either electroplating or electroless plating may be used.
In the multilayer ceramic substrate 14 thus obtained, since the second base layers 2 in which Ag easily diffuses may be disposed only at places in contact with the restriction layers 10 and 11, Ag does not easily diffuse in the entire multilayer ceramic substrate 14. Hence, degradation in electrical properties, such as degradation in insulating reliability, caused by the Ag diffusion can be suppressed to a minimum level.
As shown in a cross-sectional view of
As described above, when the multilayer ceramic substrate 14 is formed in a collective substrate state, a division step is preferably performed after the surface mount electronic devices 15 and 16 are mounted.
Heretofore, although the present invention has been described with reference to the preferred embodiments shown in the figures, other various preferred embodiments may be performed within the scope of the present invention.
For example, in the preferred embodiment shown in the figures, the second base layers 2 are disposed along the two primary surfaces of the unsintered ceramic laminate 12 or the multilayer ceramic substrate 14, and the restriction layers 10 and 11 are disposed along the two primary surfaces of the composite laminate 13; however, when the restriction layer is disposed only along one primary surface of the composite laminate, the second base layer may be disposed only along the primary surface at the side at which this restriction layer is disposed.
In addition, the number of the first base layers 1 and that of the second base layers 2, in particular, the number of the first base layers 1, may be arbitrarily changed in accordance with required design.
In addition, the present invention may also be applied to a multilayer ceramic electronic device having a different function as well as the multilayer ceramic substrate.
Next, Examples performed in order to confirm the advantages of preferred embodiments of the present invention will be described.
As first base-layer green sheets and second base-layer green sheets, sheets containing an alumina powder and a borosilicate glass powder at a ratio of 60:40 were prepared. The composition ratio of the borosilicate glass contained in the first base-layer green sheets and that of the borosilicate glass contained in the second base-layer green sheets were set as shown in Table 1.
As shown in Table 1, the amount of B2O3 of the borosilicate glass contained in the second base-layer green sheet was set larger than that of the borosilicate glass contained in the first base-layer green sheet, and hence the softening point of the glass of the former was set lower than that of the glass of the latter.
In addition, as restriction-layer green sheets, sheets containing an alumina powder which had an average particle diameter of 1.0 μm and a thickness of 300 μm were prepared.
Subsequently, an appropriate number of the first base-layer green sheets and an appropriate number of the second base-layer green sheets were respectively laminated so that the total thickness of a first base layer portion was 300 μm and the total thickness of one of second base layer portions, which sandwiched the first base layer portion in a lamination direction, was 15 μm, thereby forming an unsintered ceramic laminate. Furthermore, the restriction-layer green sheets described above were laminated so as to sandwich this unsintered ceramic laminate in the lamination direction and were then pressure-bonded, thereby forming an unsintered composite laminate.
When the above unsintered ceramic laminate was formed, two microstrip lines were formed therein as a conductive pattern primarily composed of Ag, so that a bandpass filter combined with a 5-GHz resonator was formed.
Next, after the above composite laminate was fired at a temperature of 900° C., the restriction layers were removed by wet blast, so that a multilayer ceramic electronic device of the Example within the scope of the present invention was obtained.
On the other hand, as a multilayer ceramic electronic device out of the scope of the present invention which was used for comparison purposes, an electronic device in which the above first base-layer green sheets were only laminated (Comparative Example 1) and an electronic device in which the above second base-layer green sheets were only laminated (Comparative Example 2) were formed.
First, when the bonding force generated by the restriction layer of each of the Example and Comparative Examples 1 and 2 thus obtained was evaluated, according to the Example and Comparative Example 2, so-called non-shrinkage firing (rate of shrinkage=dimension after firing/dimension before firing=99.9%) was realized; however, according to Comparative Example 1, the restriction by the restriction layer did not sufficiently work, and a large shrinkage was generated.
In addition, when filter characteristic values of the Example and Comparative Example 2 were evaluated, the insertion loss was 0.5 dB according to the Example; however, the insertion loss was increased to 1.0 dB according to Comparative Example 2.
In addition, when an Ag diffusion amount according to the Example was evaluated by a mapping analysis using WDX, it was confirmed that the Ag diffusion amount of the second base layer portion was large as compared to that of the first base layer portion.
As for removability of the restriction layer, a significant difference between the Example and Comparative Examples 1 and 2 was not observed since the restriction layers containing an alumina powder which had the same average particle diameter were used.
While preferred embodiments of the present invention have been described above, it is to be understood that variations and modifications will be apparent to those skilled in the art without departing the scope and spirit of the present invention. The scope of the present invention, therefore, is to be determined solely by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2008-037646 | Feb 2008 | JP | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2009/052726 | Feb 2009 | US |
| Child | 12606332 | US |
