JPS62252004A - Glass ceramic sintered body - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a glass-ceramic sintered body obtained by firing a powder compact containing a mixture of glass powder and filler powder.

[Background technology]

2. Description of the Related Art In recent years, the use of multilayer wiring boards made of ceramic materials has been expanding as demands for miniaturization and high reliability have increased in multilayer wiring boards on which highly integrated LSIs and a large number of various elements are mounted.

The ceramic multilayer wiring board is formed by forming a green sheet using alumina as the main material, and on the green sheet, conductor wiring made of a high melting point metal (Mo, W, etc.) is printed by thick film technology. Thereafter, a multilayer green sheet obtained by laminating these green sheets together is fired in a high-temperature non-oxidizing atmosphere at about 1500-1600°C.

However, in the multilayer wiring board mainly made of alumina as described above, the high dielectric constant of alumina and the high resistance of the miniaturized wiring conductor (high melting point metal such as Mo or W) prevent propagation through the multilayer wiring. It took a long time for the signal to be transmitted, making it difficult to meet the demand for higher speeds.

To solve this problem, low resistance metal materials (Au, Ag, Ag Pd
, Cu, etc.) may be used to form finer interconnections. However, each of the above-mentioned low-resistance metal materials has a melting point of around 1000° C., which is much lower than the firing temperature of the substrate when alumina is used as the main material, so it cannot be used in practice.

In order to solve the above problems, multilayer wiring boards made of glass or glass powder sintered bodies (glass-ceramic bodies) have been developed. In the case of this substrate, the temperature during firing is
This is much lower than the firing temperature of the substrate mainly made of alumina. Therefore, A u , A g s A g
Even if a low-resistance metal material such as P d s Cu is used, it is possible to prevent the wiring pattern from melting before sintering, shrinking due to surface tension, and causing disconnection or connection with other wiring.

The glass used for this substrate is typically 5iOz −'
Alx 05-MgO-based calasteate, (-(7) composition is S i 0tSA1□0., MgO as the main component, and Z n O% L iz OlL i F,
A nucleating agent such as Pg 05 and BiOs, PiO
A metal compound such as Ss L rtO that contributes to vitrification and works to increase the degree of sintering is added as a subcomponent. Specifically, Japanese Patent Publication No. 59-46900, Japanese Patent Application Publication No. 51-52422, and Japanese Patent Application Publication No. 59-92943.
It is stated in the issue bulletin etc.

However, the glass powder sintered bodies disclosed in Japanese Patent Publication No. 59-46900 and Japanese Patent Application Laid-open No. 51-52422 contain I, lto, and LtF as nucleating agents, so that the L i + ion There is a problem in that sufficient insulation cannot be maintained due to the migration silane phenomenon. In addition, when Li+ ions enter the glass component,
There is also the problem that crystals of β-subodumene and β-eucryptite, which have a high dielectric constant, are likely to precipitate, increasing the dielectric constant of the entire substrate.

[Purpose of the invention]

In view of these circumstances, the present invention provides a glass-ceramic sintered body that is sufficiently densified by firing at a low temperature of 1000°C or less, has a low dielectric constant, and is suitable for forming wiring using low-resistance metal materials. The purpose is to provide

[Disclosure of the invention]

In order to achieve the above object, the inventors conducted intensive studies to improve the performance of sintered bodies by combining a new type of glass (crystallizing glass) and filler.As a result, After discovering something like this, I completed this invention.

That is, S i Ots A 1 t Os and M
The weight percent composition of gO consisting of only three components is
45≦Sin, ≦60.15≦AltO3≦35.20
They are blended and melted so that ≦Mgo≦30. This melt is rapidly cooled so as not to precipitate crystals to obtain a transparent glass, and then finely pulverized to an average particle size of about 1 to 10 μm to obtain glass powder. The sintered body obtained by mixing this glass powder and a ceramic filler powder with even better electrical properties and firing the molded body is dense and has a low dielectric constant.
Moreover, this can be achieved even at a firing temperature of 100° C. or lower.

Therefore, the present invention provides a glass ceramic sintered body obtained by firing a powder compact in which a glass composition powder and a filler powder are mixed, wherein the composition of the glass composition is 510145 to 60% by weight. , AI! a
s 5 to 35% by weight, MgO 20 to 30% by weight, and the ratio of the glass composition to the filler is 80 to 95% by weight of the glass composition and 5 to 20% by weight of the filler. The glass ceramic sintered body according to the present invention will be explained in detail below, focusing on the sintered body.

The reason why the composition ratio of the glass composition used in this invention is limited as described above is because if the composition ratio of SiO□ exceeds 60% by weight, the melting temperature of the glass composed of the above three components increases. Not only does this result in significant crystallization during firing, the surface layer of the glass powder rapidly crystallizes, and the glass component (phase) that enhances sintering is insufficient, making it impossible to form a dense sintered body. If it is less than 45% by weight, the crystallization temperature of the glass powder will rise, and the required firing temperature will also rise accordingly. becomes an unsintered state.

When the composition ratio of A1!03 exceeds 35%, the frit obtained by rapidly cooling the melt tends to devitrify (crystallize), and the firing temperature exceeds 1300°C, resulting in a dense sintered body. The temperature range that can be obtained becomes extremely narrow. 15% by weight
When it is below , the main crystal phase becomes Sin, -MgO-based crystals (enstatite, forsterite), the amount of crystals itself decreases significantly, the dielectric constant increases, and the mechanical strength of the sintered body itself becomes weak. turn into.

When the composition ratio of MgO exceeds 30% by weight, the temperature
If the firing temperature is lower than that, not only will sintering not be possible, but the amount of crystals will also decrease. If it is less than 20%, the glass melting temperature will rise and the frit obtained by rapidly cooling the melt will also tend to devitrify. Not only that, when the molded body is fired, crystallization is remarkable, and the surface layer of the glass powder rapidly crystallizes, causing the glass component (phase) that increases sintering to occur.
is insufficient, making it impossible to form a dense sintered body.

The glass composition used in this invention includes Li, Na, KSP
It does not contain elements with relatively high ionic conductivity such as b.

The filler used in this invention is not particularly limited, but may be at least one selected from α-quartz, fused silica, silica such as cristobalite, cordierite, and/or steatite, forsterite, and quartz. Examples include at least one type selected from lastite, anorthite, alumina, and celsian.

The filler not only increases the mechanical strength of the sintered body but also decreases the dielectric constant. If the proportion of filler added exceeds 20% by weight, sintering will become difficult and sintering at temperatures below 1000°C will not be possible. Further, the bulk of the sintered body contains many bores. 5
If it is less than % by weight, the effects of adding the filler, such as lowering the dielectric constant, adjusting the coefficient of thermal expansion, and improving the thermal conductivity, will not be observed.

If a filler that does not contain the above-mentioned elements with relatively high ion conductivity is used, even if the sintered body is used as a multilayer wiring board material, there is no risk of deterioration of insulation due to migration phenomenon.

The powder of the above-mentioned glass composition is obtained by, for example, blending and melting each component so that the weight percent composition is within the above-mentioned range, and then rapidly cooling the melt so as not to precipitate crystals to obtain a transparent glass. Although it can be obtained by finely pulverizing it, it may also be obtained by other methods. The particle size of the powder of the glass composition is
Although not particularly limited, it is preferable that the average particle size is 1 to 10 μm. If the average particle size exceeds 10 μm, the surface unevenness of the glass ceramic sintered body becomes severe, and when used as a wiring board, the conductor accuracy of the circuit may deteriorate.

Also, since the crystallization temperature may become high,
If the temperature is lower than 0.degree. C., sufficient crystal precipitation will not occur, resulting in a sintered body with a low amount of crystals, so there is a possibility that a reduction in dielectric constant cannot be expected. At the same time, the mechanical strength may become low, which may lead to a lack of practicality. On the other hand, if it is less than 1 μm, the crystallization rate of the glass composition may accelerate, and the crystallization may end before sufficient sintering occurs, making it difficult to increase the sintered density. There is.

The particle size of the filler is also not particularly limited, but it is preferably set approximately equal to or slightly smaller than the particle size of the glass composition.

The method of mixing the glass composition and filler is not particularly limited, and may be wet or dry. When an organic substance such as a resin or a solvent is used to obtain a molded body, it is preferable to perform pre-firing in advance to remove the organic substance, and then carry out firing for sintering. In addition,
The organic substance is not particularly limited, and various types can be used. Moreover, materials other than organic substances may be used, or a molded article may be obtained without using anything.

Examples of the powder molded body in which the powder of the glass composition and the filler are mixed include, but are not limited to, a green sheet or a stack of a plurality of green sheets.

The conditions for firing the molded body are not particularly limited, but since sintering can be performed at a temperature lower than the melting point (around 1000°C) of the above-mentioned low-resistance metal material, it is recommended that the molded body be fired at that temperature. For example, a low-resistance metal material can be printed and fired simultaneously. Simultaneous firing is not required, and the application is not limited to wiring boards such as multilayer wiring boards.

Next, the glass ceramic sintered body according to the present invention will be explained in detail based on Examples.

5iOz prepared in the proportions shown in glass frits G-1 to G-9 (G-8 and G-9 are for comparative examples) in Table 1.
, AI, O, and MgO (7) were placed in an alumina crucible and heated to approximately 1500°C.
It melted under a heating temperature of .

The melt thus obtained was dropped into water to obtain a glass composition (frit). This composition was sufficiently pulverized wet or dry in an alumina ball mill to obtain a glass powder having an average particle size of 1 to 10 μm.

Examples 1 to 20 and 4 of Table 2 were added to this glass powder.
Filler powder was mixed in the proportions shown in Comparative Examples 1 to 8 in the table,
Further, as an organic binder, for example, polybutyl methacrylate oyster fat, dibutyl phthalate, xylene, etc. were added and kneaded, followed by defoaming treatment under reduced pressure. Thereafter, using this kneaded body, a continuous sheet having a thickness of 0.2 was produced on a film sheet by a doctor blade method. After drying this, it was peeled off from the film sheet and punched out into five crane squares to produce a green sheet.

A plurality of these green sheets were stacked and molded using a mold press to form a molded body, which was then fired. 200℃ during firing
The temperature was raised to a temperature of 850 to 100° C. shown in Tables 3 and 5, respectively, at a rate of 200° C./hour, and after this state was maintained for 3 hours, the temperature was lowered at a rate of 200° C./hour.

Examples 1 to 2o and Comparative Examples 1 to 8 thus obtained
The dielectric constant (relative permittivity) and water absorption of the sintered bodies were measured, and the results are shown in Tables 3 and 5. In addition,
The presence or absence of devitrification (crystallization), thermal expansion coefficient, and thermal conductivity during glass lift fabrication are also shown. Measurement of relative permittivity is performed using IM
It was performed at a frequency of Hz. Measurement of water absorption rate is based on JIS C-
2141.

As shown in Tables 1 to 5, the sintered bodies of Examples 1 to 20 are extremely dense compared to the sintered bodies of Comparative Examples 1 to 8, despite being fired at a temperature of 1000°C or less. A good sintered state is achieved. The dielectric constant is also a sufficiently small value for practical use. Thermal expansion coefficient and thermal conductivity are also good.

Note that the sintered bodies of Comparative Examples 1 to 8 did not become dense sintered bodies unless they were fired at a temperature of 1100° C. or higher. In addition, since the sintered bodies of Comparative Examples 1 to 8 are not in a dense sintered state, the relative dielectric constant value appears to be a higher value (the measured value is smaller), but it is not the true value of the material itself. Therefore, the relative permittivity is not displayed in other comparative examples.

〔Effect of the invention〕

As described above, the glass ceramic sintered body of the present invention is made by firing a powder compact in which the powder of the glass composition having the above composition and the filler powder are mixed in the above ratio, so that it is dense. Moreover, this sintered body not only has a small dielectric constant (but can be achieved at a sintering temperature of 1000°C or less). It is suitable as a wiring board material, and since the firing temperature is 1000° C. or less, it is also possible to print a low-resistance metal material and simultaneously bake it to form wiring.

Claims (4)

[Claims] (1) A glass ceramic sintered body obtained by firing a powder compact in which a glass composition powder and a filler powder are mixed, wherein the composition of the glass composition is SiO
_245 to 60% by weight, Al_2O_315 to 35% by weight, MgO 20 to 30% by weight, and the ratio of the glass composition to the filler is 80 to 95% by weight of the glass composition.
, a glass ceramic sintered body characterized by having a filler content of 5 to 20% by weight. (2) A patent claim in which the filler is at least one member selected from the group consisting of α-quartz, fused silica, cristobalite, cordierite, steatite, forsterite, wollastonite, anorthite, alumina, and celsian. The glass ceramic sintered body according to scope 1. (3) The glass ceramic sintered body according to claim 1 or 2, wherein the firing is performed at a temperature of 1000° C. or lower. (4) The glass ceramic sintered body according to any one of claims 1 to 3, wherein the glass composition powder has an average particle size of 1 to 10 μm. (5) The filler powder has an average particle size of 1 to 10 μm. The glass ceramic sintered body according to any one of claims 1 to 4, which has a particle size of 1 to 10 μm.