JPH08333157A - Wiring substrate, its production, amorphous glass, ceramic composition for wiring substrate, electronic circuit device, module for electronic computer and electronic computer - Google Patents

Abstract

PURPOSE: To obtain a ceramic wiring substrate having small dielectric constant, a thermal expansion coefficient matching with silicon and high in flexural strength and its production by sintering at 900-1050 deg.C. CONSTITUTION: A glass having 850-1100 deg.C softening temperature, that is, a glass having a composition expressed by points inside the region surrounded by the lines respectively binding the points respectively exhibiting a first, third, 10th, 11th and fourth compositions (containing the regions on the lines) in figure 1 (an SiO2 -B2 O3 -R2 O system triangular composition). Each position of the small circle exhibits its composition and the number in the small circle exhibits the composition number) is used as a raw material. Water-based dispersing particles are used as the binder and a green sheet is pressed in the thickness direction in a baking process.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wiring board and a technique for providing the wiring board, and in particular, an organic binder is used as a binder and a base metal conductor material such as copper is used as a conductor.
The present invention relates to a wiring board suitable for high-density wiring, a method for manufacturing the wiring board, and an amorphous glass and a ceramic composition for manufacturing the wiring board.

[0002]

2. Description of the Related Art Ceramic wiring boards are used as substrates for mounting semiconductor chips and small electronic components because they can be miniaturized and have high reliability, and are used in electronic computers, communication devices, home appliances, etc. It has been incorporated.

Among the ceramic wiring boards, wet ceramic wiring boards using green sheets are often used because they are advantageous for high-density wiring. This wet ceramic wiring board is manufactured by the following manufacturing method. First, a ceramic green sheet (hereinafter referred to as a green sheet) in which ceramic raw material powders are combined with an organic resin is produced, and then a through hole is formed in this green sheet, and then a conductor paste is used to cover the surface. In addition to forming the wiring patterns, the through holes are also filled with the conductor paste in order to connect the wiring patterns of each sheet when a plurality of sheets are laminated. Next, in this way the wiring pattern
After stacking a predetermined number of green sheets on which the sheets have been formed, stacking and laminating, and then firing. As described above, the ceramic multilayer wiring board is manufactured.

Conventionally, alumina (Al ₂ O ₃ ) has been mainly used as an insulating material for a multilayer wiring board on which a semiconductor integrated circuit element made of silicon is mounted, and a conductor material is co-fired with alumina. Molybdenum (Mo) and tungsten (W) which are refractory metals that can be bonded are used. However, the coefficient of thermal expansion of alumina is about 7 × 10 ^-6 / ° C.
Therefore, when the silicon semiconductor element is directly mounted on the alumina substrate, a large stress acts on the connecting conductor portions, and reliability cannot be obtained. Further, the relative permittivity of alumina is relatively large at about 10, and the signal propagation as a multilayer wiring board is not yet sufficiently fast. In addition, the refractory metal has a relatively high resistance.

Therefore, in order to solve the above problems, Japanese Patent Publication No. 2-49550 discloses that the content is 20% by weight or more, 50% or more.
Alumina less than wt% and 10 wt% or more, 60 wt%
Less than 40% by weight of quartz glass and a glass ceramic layer containing a mixture of 20% by weight or more and less than 40% by weight of non-crystallized glass or crystallized glass, and a copper conductor layer,
A multilayer ceramic wiring board characterized by using a binder containing a heat depolymerizable resin and a method for manufacturing the same have been proposed. Also, for example, Japanese Patent Publication No. 2-4955
No. 0 and Japanese Patent Publication No. 1-50120 disclose that a semiconductor element is mounted by using a glass / copper wiring board in which copper having a low electric resistance is combined with a conductor material and a glass ceramic having a low dielectric constant. The technology for realizing the high-speed signal transmission required for the above is described.

[0006]

A green sheet is made by molding a slurry prepared by mixing a ceramic powder, an organic binder, a solvent for the binder and a ball mill into a sheet.

As the organic binder, polyvinyl butyral resin, thermal depolymerization type acrylic resin and the like are generally used. Therefore, as the solvent, alcohol-based, ketone-based, or chlorine-based organic solvents such as trichlorethylene have been conventionally used.

However, alcohol-based and ketone-based solvents are flammable, and some of them are toxic to the human body, which poses a safety problem. In addition to these problems, the chlorine-based solvent may have an adverse effect on the environment. Therefore, from the viewpoint of safety and hygiene, it is desirable to use water or a solvent containing water as a main component instead of these organic solvents.

Therefore, an organic binder material using water as a solvent has been developed. For example, a technique using a water-soluble polyacrylic acid ester or a water-soluble polymethacrylic acid ester as a binder for ceramic molding (Japanese Patent Publication No.
-53233, Japanese Patent Publication No. 1-44668)
Alternatively, a technique in which acrylic acid or methacrylic acid is added to an emulsion-based binder obtained by emulsion-polymerizing a vinyl monomer using a surfactant and neutralized with ammonia is used (JP-A-60-180955). JP-A-60-1
No. 80956) has been proposed.

However, since an organic binder material using water as a solvent is generally added with a hydrophilic functional group, its thermal decomposability is lower than that of an organic binder material using an organic solvent, and it is difficult to remove the binder. Have.

It can be said that the burning-out (debinding) of the organic binder consists of a decomposition process of the organic resin into carbon and a carbon oxidation process. The former process occurs at a temperature of about 200 to 400 ° C, and the latter process occurs at a temperature of about 700 ° C or higher. In particular, the latter process is a reaction represented by C + 2H ₂ O → CO ₂ + 2H _2, and the higher the temperature, the easier the reaction proceeds. Therefore, when the organic binder is burned out at a temperature as high as possible, the binder can be removed in a short time and the productivity is good. In particular, in order to use copper, which is easily oxidized, as the conductor material, the binder removal step (step of burning out the organic binder for preparing the green sheet) is performed in an atmosphere in which copper is not oxidized (an atmosphere of water vapor, nitrogen, hydrogen gas, etc.). It is preferable, however, that when the binder is removed in such a non-oxidizing atmosphere, the binder residue after thermal decomposition becomes carbon,
Since it takes a very long time to remove this carbon as CO or CO ₂ by a thermodynamic reaction with water vapor, it is considered desirable to perform the binder removal step at a high temperature.

After the organic binder is burned out, the glass ceramics are heat-treated for densification, that is, sintered. In order to improve the productivity of the multilayer ceramic wiring board, those heat treatments need to be performed in a short time.

However, when the glass ceramics, which is the substrate material, is excessively sintered during the heat treatment in the binder removal step, and the residue of the organic resin and the carbon are trapped in the sheet, the trapped carbon is oxidized. The resulting gas will cause voids and increase in the dielectric constant, and the insulation resistance of the resulting glass ceramics will decrease, and the glass ceramics will not be sufficiently densified in the subsequent heat treatment, resulting in sufficient strength. It is not preferable because there are problems such as not being able to do so. Generally, the amount of carbon remaining in the substrate is preferably 200 ppm or less.

Therefore, in order to raise the temperature of the binder removal step, it is necessary to use glass having a high softening point. However, since a material that sinters at the same time with copper having a melting point of 1083 ° C. must be used, the glass material is limited to one that can be sintered at around 1000 ° C. Therefore, it is difficult to set the binder removal temperature to 800 ° C. or higher.

Further, in order to prevent the residue of the organic resin and the carbon from being trapped in the sheet, the glass ceramic as the substrate material, which does not excessively sinter during the heat treatment for burning out the organic binder. Is preferably used. As described above, the organic binder material using water as the solvent is less likely to be thermally decomposed and the binder removal rate is slower than the organic binder material using the organic solvent. Therefore, in order to use an organic binder material that uses water as a solvent, a glass ceramics suitable as a substrate material is necessary.

Further, in order to improve the performance and reliability of the above-mentioned multilayer ceramic wiring board for mounting a silicon semiconductor integrated circuit element, the ceramic material of the board is made of copper so that low-resistance metal copper can be used as a conductor. Below 1050 ° C, which is lower than the melting temperature of 1083 ° C (preferably 1
Sintering at around 000 ° C), low relative permittivity, and coefficient of thermal expansion of silicon (3.0 × 10
^-6 / ° C.) And have a large bending strength. Borosilicate glass-filler type is mentioned as a ceramic material satisfying these characteristics.

However, in the borosilicate glass / filler system,
The water resistance of borosilicate glass when it is made into a green sheet becomes a problem. If the water resistance of borosilicate glass is poor, the contained boron oxide easily elutes in water, and in a high humidity atmosphere,
Boric acid crystals are deposited on the glass surface. In addition, some borosilicate glasses are likely to precipitate cristobalite crystals by heat treatment. Cristobalite crystals are about 230
Since a crystal phase transition accompanied by an abnormally large volume change occurs at 0 ° C., it causes cracking of the substrate and its precipitation is not preferable.

Further, the conventional technique has a problem that it is not possible to perform sufficient high-density wiring.

As a measure of the wiring density, there is an interval between through holes (through hole pitch) in the green sheet. The pitch limit, that is, the wiring density limit is determined by the positional accuracy of the opened through holes, and the positional accuracy is determined by the mechanical properties of the green sheet such as tensile strength and shear strength.
Therefore, in order to increase the wiring density, a green sheet having mechanical properties superior to those of the prior art is required. For that purpose, it is necessary to develop a material capable of obtaining a green sheet having excellent mechanical properties and a green sheet forming process.

Further, in the conventional sintering technology, variations in particle size and composition of ceramic powder raw materials, variations in green sheet density, mismatch in sintering shrinkage curve between ceramic material and copper conductor, pattern density of copper conductor, and lamination pressure bonding process. The dimensional accuracy of the sintered substrate is not sufficient because there are variations in the sintering contraction rate due to the raw materials and processes, such as variations in the stack density in the stack, variations in the atmosphere and temperature during the firing process, etc. Was hindering In addition, high dimensional accuracy is required to mount the thin film wiring board. However, in order to greatly improve the dimensional accuracy of the sintered body, it is necessary to develop a new wiring board manufacturing process different from the conventional one.

Therefore, the present invention solves the above-mentioned problems, uses an aqueous solvent as a solvent, and easily removes the binder,
It is an object of the present invention to provide a wiring board capable of high-density wiring and having high dimensional accuracy, a method for manufacturing the wiring board, and a material for manufacturing the wiring board.

[0022]

The wiring board as described above is made of a borosilicate glass having a high softening point and good water resistance, and a glass material for a board made of a ceramic filler. Also, it can be obtained by using a water-based dispersion type binder resin that has a small dimensional change in the printing process and performing pressure sintering with almost no dimensional change.

In the present invention, in order to achieve the above object,
A method of manufacturing a wiring board having the following steps (1) to (4) in this order, a material used in this method, a wiring board manufactured by this method, an electronic circuit device including the wiring board, and a computer. Module and an electronic calculator are provided.

(1) A slurry preparing step of preparing a slurry by mixing amorphous glass, a filler, an organic binder, and a solvent (2) Green for preparing a green sheet by processing the slurry into a sheet shape Sheet preparation step (3) Conductor forming step of forming via holes and / or wiring with conductors on the green sheet (4) Step of laminating the green sheet as necessary (5) Heating the laminated body to 700 to 880 ° C (6) Heating step of heating the laminated body to 900 to 1050 ° C. to sinter it. However, the above amorphous glass includes SiO ₂ , B ₂ O ₃ , and R ₂
O (R represents an alkali metal) and unavoidable impurities are contained, and in the SiO ₂ —B ₂ O ₃ —R ₂ O system triangular composition diagram shown in FIG. 1, a point indicating the first composition and a third composition. Showing a third composition and a tenth composition,
A point indicating the tenth composition and a point indicating the eleventh composition, a point indicating the eleventh composition and a point indicating the fourth composition, a point indicating the fourth composition and a point indicating the first composition. It has a composition indicated by a point within a region (including on the line) surrounded by connecting lines. However, in FIG. 1, points indicating each composition are represented by small circles, and the numbers in the small circles indicate the numbers of the compositions represented by the small circles.

It should be noted that the triangular composition diagram is 3 by the triangular coordinate.
It is a figure expressing the composition of a component system. In the triangular composition diagram, the vertices of an equilateral triangle (denoted as A, B, and C) represent pure substances of any of the three components, and the points within the equilateral triangle (including the sides) represent the three components. Represents a composition consisting of at least one of these. The ratio of each component contained in the composition is represented by the ratio of the lengths of perpendicular lines drawn from the point (P) indicating the composition to the opposite side of each vertex. That is, assuming that the opposite side of the vertex A is a, the ratio of the component indicated by the vertex A is represented by the length of a perpendicular line (denoted by h) from the point P to the side a. The length of the line segment h (that is, the composition ratio of the components indicated by the vertex A) is calculated from the point P by the line segment h.
It can be known by drawing a line perpendicular to the line, obtaining the intersection of this line and the side with the percentage (or fraction) scale of the component indicated by the vertex A, and reading the scale of the intersection.

Further, each component of the amorphous glass is converted into an oxide. That is, the amount of the SiO ₂ component is an amount obtained by converting the amount of silicon contained in the amorphous glass into silicon oxide (SiO ₂ ), and the amount of the B ₂ O ₃ component is not R ₂ is an amount obtained by converting the amount of boron contained in the crystalline glass into boron oxide (B ₂ O ₃ ).
The amount of the O component is the amount obtained by converting the amount of the alkali metal contained in the amorphous glass into the alkali metal oxide (R ₂ O), and the amount of the Al ₂ O ₃ component is The amount of aluminum contained in the amorphous glass is an amount obtained by converting it into aluminum oxide (Al ₂ O ₃ ), and the amount of ZnO component is the amount of zinc contained in the amorphous glass. , Zinc oxide (ZnO).

The composition ratio of each composition is as follows: SiO ₂ component, B ₂ O ₃
When the total weight of the component and the R ₂ O component is 100%, the first composition is 88% by weight of the SiO ₂ component and B ₂ O ₃
In the third composition, the SiO ₂ component is 82% by weight and the B ₂ O ₃ component is 18% by weight.
In the composition of, the SiO ₂ component is 84 wt% and the B ₂ O ₃ component is 1
0% by weight, R ₂ O component is 6% by weight, and the 11th composition is 90% by weight of SiO ₂ component, 5% by weight of B ₂ O ₃ component, 5% by weight of R ₂ O component, The fourth composition is Si
89% by weight of O ₂ component, 10% by weight of B ₂ O ₃ component, R ₂ O
The component is 1% by weight.

In the above composition range, the point indicating the fourth composition, the point indicating the fifth composition, the point indicating the fifth composition, the point indicating the ninth composition, and the ninth composition are shown. And a point indicating the tenth composition, a point indicating the tenth composition, a point indicating the eleventh composition, a point indicating the eleventh composition and a point indicating the fourth composition, respectively. The composition indicated by the dots within the region surrounded by the line (including on the line) is more preferable.

In the fifth composition, the SiO ₂ component is 8
7% by weight, 11.5% by weight of B ₂ O ₃ component and 1.5% by weight of R ₂ O component, and the ninth composition is SiO 2.
_The composition has 84.7% by weight of ₂ components, 10.8% by weight of B ₂ O ₃ component and 4.5% by weight of R ₂ O component.

From the viewpoint of water resistance of glass, R is preferably potassium. Further, the R ₂ O in the composition described above, R ₂ O and R ₂ O molar amount of 90% or less of Al ₂ O
A glass having a composition replaced with ₃ is more preferable, and may further contain 1 to 4% by weight of ZnO component with respect to the entire amorphous glass.

The amounts of the amorphous glass and the filler are 60 to 95% of the amorphous glass and 40 to 5 volume of the filler when the volume of the amorphous glass and the filler is 100% by volume. % Is preferable.

Further, in the present invention, as the organic binder,
An organic binder for ceramic molding obtained by suspension polymerization using a water-soluble polymer as a dispersion stabilizer for polymerization, that is, (A) at least one or more acrylic ester or methacrylic ester (provided that the carbon number is 1 to 1).
18 alkyl groups, esters of cyclic alkyl groups or aryl groups having 1 to 12 carbon atoms) 100 parts by weight,
(B) 1 to 9.5 parts by weight of a water-soluble polymer (dispersion stabilizer for polymerization) is dissolved in water or a mixed solution of water and a water-soluble organic solvent to prepare a solution of (A) in the presence of a polymerization initiator. A polymer compound obtained by suspension (co) polymerization of an ester compound is used.

Further, in the present invention, in the step (6), it is desirable to apply a pressure in the thickness direction when the molded body (the laminated body when laminated, the green sheet when not laminated) is sintered. By doing so, it is possible to suppress and control the shrinkage of the molded body in the direction perpendicular to the thickness direction by the frictional force or the restraining force generated on the surface.

[0034]

FIG. 2 schematically shows an example of the method of manufacturing the wiring board of the present invention. The method shown in FIG. 2 is (1)
As shown in (a), a slurry process of putting a glass ceramic composition consisting of amorphous glass and a filler, an organic binder, and a solvent into a ball mill device 1 and mixing them to form a slurry, (2) FIG. As shown in (b), the slurry 2 is processed into a sheet by a casting machine 3 to form a green sheet 4, and (3) a green sheet obtained as shown in FIG. 2 (c). A punching step of forming a through hole 51 in the sheet 4 by using the punch 5, and (4) as shown in FIG. 2D, the conductive paste 7 placed on the green sheet 4 is penetrated through the green sheet 4 by a squeegee 6. The via hole 53 is filled in the hole 51.
And forming a wiring 52 by printing a conductor paste on the surface layer of the green sheet, and (5) FIG.
As shown in (e), a laminating step of laminating a plurality of green sheets 4 each having the via hole 53 and the wiring 52 obtained in FIG. 2 (d) and adhering them to form a green sheet laminated body 41; ) As shown in FIG. 2 (f), the obtained green sheet laminate 41 is heated to 700-
A binder removal step of heating to 880 ° C. and binder removal;
Furthermore, it has a sintering step of sintering at 900 to 1050 ° C. in this order. The details will be described below.

<Glass-ceramic composition> a. Softening temperature The glass-ceramic composition that constitutes the green sheet of the present invention (that is, used in the slurrying step) is a composite of glass particles and filler particles, and such a composite is formed by heating the glass by heat treatment. Softens and flows, and the contact portion of the glass particles increases to reduce the surface area of the glass particles, that is, the sintering of the glass particles occurs. The temperature at which glass softens and flows and sintering occurs
It depends on the softening temperature of the glass, the amount of filler mixed with the glass particles, the particle size of the glass particles and the filler particles, and the like. Generally, the filler hinders the sintering of the glass particles, so that the larger the amount of the filler, the less likely the glass particles will sinter.

As described above, it is preferable that the glass particles are less likely to be sintered during the heat treatment for burning out the organic binder contained in the green sheet. Therefore, it is possible to increase the amount of the filler. However, when the amount of the filler is too large, it becomes difficult for the glass to be densified and sintered. The heat treatment temperature for densification and sintering is limited to 1050 ° C. or lower, which is slightly lower than the melting point of copper, 1083 ° C. Therefore, if densification and sintering is difficult, heat treatment for a long time, or heat treatment while applying pressure. However, such heat treatment is not preferable in terms of productivity of the multilayer ceramic wiring board.

As a glass composition of glass ceramics for a multilayer ceramic wiring board, borosilicate glass typified by Pyrex glass (trade name of Corning Co.) is used from the viewpoint of the coefficient of thermal expansion and the relative dielectric constant required as substrate characteristics. Used. The composition of Pyrex glass is SiO ₂ : 8
1% by weight, B ₂ O ₃ : 12% by weight, Na ₂ O: 4% by weight,
Al ₂ O ₃ : 3% by weight, and the softening temperature is 821 ° C., which is one of the highest softening temperature among commercially available borosilicate glasses. Borosilicate glass having a softening temperature equal to or higher than that of Pyrex glass has a high manufacturing cost and is difficult to obtain as mass-produced commercial glass.

The inventors of the present invention studied the production of a multilayer ceramic substrate using Pyrex glass, and because the softening temperature was too low, if the amount of the filler was small, the binder removal step (700 to 880 ° C. in a non-oxidizing atmosphere) was performed. In the heat treatment), the sintering of the glass particles proceeded, the organic binder residue was taken into the glass, and it was difficult to completely remove the binder. On the other hand, when the filler amount was increased to 50% by volume or more, the sintering of the glass particles was suppressed, and the binder removal became easy. However, if the amount of filler is increased in this way, it is difficult to densify and sinter, and even if it is fired at a high temperature of 1050 ° C.
It took a long time of 0 hours or more.

If the binder is removed at a temperature lower than the softening point, carbon will not be taken into the glass. On the other hand, since it is necessary to perform simultaneous sintering with copper (melting point 1083 ° C.), it is necessary to use glass that is sintered at around 1000 ° C.

Therefore, in the present invention, the softening point is 850 ° C.
Glass at 1100 ° C. is used. If the softening temperature is 850 ° C. or higher, the progress of sintering due to heating during binder removal hardly occurs. If the softening temperature is lower than 1100 ° C.,
This is because it is possible to densify and sinter by firing at 1050 ° C. or less.

Even if glass having a softening point of less than 800 ° C. is used, if the amount of filler added is increased, the shrinkage curve due to sintering becomes gentle and the densification temperature becomes high. Therefore,
Since the densification temperature can be made higher than 800 ° C. by increasing the amount of filler, it seems that the binder removal can be performed at 800 ° C. before the densification. However, focusing on the individual glass particles, the binder removal temperature is equal to or higher than the softening point of the glass, so that the glass particles are already softened in the binder removal step and carbon is trapped inside. Therefore, the softening point of the glass is preferably equal to or higher than the carbon removal reaction temperature.

B. In order to obtain a slurry for producing a green sheet by using a solvent containing water-resistant water as a main component, it is necessary to use glass having high water resistance, that is, glass components do not elute during ball mill mixing.

Boron oxide component (B
₂ O ₃ ) easily dissolves in water. If this component elutes in the solvent during ball mill mixing, not only the B ₂ O ₃ component in the glass component will decrease, but also several tens of μm after forming the green sheet.
As boric acid crystals of the size of m, the eluted B ₂ O ₃ component is deposited on the surface of the green sheet. The deposited boric acid crystal causes a disconnection or a short circuit when forming a fine wiring having a wiring width of 100 μm or less. Similarly, when using a glass material with poor water resistance when storing the green sheet,
Boric acid crystals are precipitated by moisture absorption. Further, if the borosilicate glass has poor water resistance, B ₂ O ₃ is likely to be dissolved in water even if it becomes a sintered body, and boric acid crystals are deposited on the surface in a high humidity atmosphere, which deteriorates the strength of the substrate. . For the above reasons,
The glass used in the present invention needs to have good water resistance.

As a measure of water resistance, the amount of B ₂ O ₃ eluted per surface area of glass when the glass is immersed in pure water at 90 ° C. for 8 hours can be used. This elution amount is preferably 1.9 mg / m ² (elution amount of the Pyrex glass) or less, and more preferably 1.5 mg / m ² or less. The amorphous glass of the present invention satisfies the water resistance standard (1.9 mg / m ² or less), and particularly, the glass in which R ₂ O is K ₂ O has excellent water resistance.

C. Cristobalite Crystal Precipitability When the above-mentioned Pyrex glass, which is a commercially available borosilicate glass, is heated to around 1000 ° C., cristobalite crystals are precipitated. Cristobalite crystals are 2
Since a large volume change occurs due to the crystal phase transition at around 30 ° C., it causes cracks and lowers the substrate strength. Therefore,
It is preferable to use glass in which cristobalite crystals are hard to precipitate.

D. Dielectric constant and thermal expansion coefficient Further, the borosilicate glass of the present invention has a small dielectric constant,
It has the effect of speeding up signal propagation as a multilayer wiring board.
Further, the borosilicate glass of the present invention has a small thermal expansion coefficient,
In combination with the added filler, the coefficient of thermal expansion can be matched to that of silicon. The ceramic composition of the present invention is preferable because cristobalite crystals do not precipitate from the borosilicate glass even by the above heat treatment. Since the thermal expansion coefficient of silicon is 3.0 × 10 ⁻⁶ / ° C., the thermal expansion coefficient of the ceramic sintered body is preferably 2.0 to 4.0 × 10 ⁻⁶ / ° C.

E. Amorphous glass of the present invention, the composition of the amorphous glass of the present invention, from the viewpoint of a glass material having excellent characteristics such as the above-mentioned softening temperature, water resistance, thermal expansion coefficient, cristobalite crystal precipitation, and relative dielectric constant, It was obtained by a search experiment.

The first composition region of the amorphous glass of the present invention is as shown in FIG. 1 in the SiO ₂ —B ₂ O ₃ —R ₂ O system triangular composition diagram, where SiO ₂ is 88 and B ₂ O ₃ is 88% by weight. Is 12 for the first composition, SiO ₂ is 82, B ₂ O ₃ is 18 for the third composition, SiO ₂ is 84, B ₂ O ₃ is 10, R ₂ O.
The composition of 6 is the 10th composition, the composition of SiO ₂ is 90, and the composition of B ₂ O is
_The composition in which ₃ is 5 and R ₂ O is 5 is the 11th composition, SiO ₂
Is 89, B ₂ O ₃ is 10, and R ₂ O is 1 and the fourth composition is the fourth composition, a straight line connecting the points indicating the first composition and the third composition and the third composition First point of composition
A straight line connecting the points indicating the 0 composition, a straight line connecting the points indicating the tenth composition and the eleventh composition, and a line connecting the points indicating the eleventh composition and the fourth composition , A composition range indicated by a range (including a composition on a line) surrounded by a straight line connecting a point indicating the fourth composition and a point indicating the first composition.

The glass having a composition contained in this composition range has a softening temperature of 850 to 1100 ° C., a water resistance of a practical level, and a thermal expansion coefficient which can be matched with that of silicon by adding a filler. In the green sheet prepared by using the amorphous glass in this range, it is difficult for the glass particles to sinter in the binder removal step (heat treatment in a non-oxidizing atmosphere at 700 to 880 ° C.), and as described above, Even when a water-soluble organic binder, which hardly decomposes, is used, the binder can be easily removed without the organic binder residue being taken into the glass. Moreover, the green sheet prepared from the ceramic composition of the present invention can be densified and sintered in the step of densification and sintering even by firing for a short time (2 hours) at 1050 ° C. or less.

[0050] Here, SiO ₂ and B ₂ O ₃ forms a network structure of the glass, increase of the SiO ₂ component amount increases the softening temperature, has the effect of increasing the water resistance, increase in B ₂ O ₃ component amount Has the effect of lowering the softening temperature and water resistance. R ₂
O as a network modifying component has a function of lowering the softening temperature and enhancing the water resistance of B ₂ O ₃ in a part of the composition range. Those compositions SiO ₂ is larger than the amorphous glass of the present invention, sintering at around 1000 ° C. and a softening temperature becomes too high it is difficult, also, B ₂ O ₃ in many compositions ones, B _{Since the} amount of ₂ O ₃ eluted is too large, it is inferior in water resistance, and the composition having a large amount of R ₂ O has a too large coefficient of thermal expansion and therefore has a large difference in coefficient of thermal expansion from the LSI chip. Not fit for purpose.

A glass having a composition on the side with more SiO ₂ than the line connecting the first composition, the fourth composition and the eleventh composition is
The softening temperature is too high, which is not preferable in achieving the object of the present invention. Further, a glass having a composition on the side containing more R ₂ O than the line connecting the eleventh composition and the tenth composition is too high in thermal expansion coefficient and is not preferable for achieving the object of the present invention. A composition having less SiO ₂ than the line connecting the third composition and the tenth composition has an excessively large B ₂ O ₃ elution amount, and is not preferable for achieving the object of the present invention.

The second composition range of the amorphous glass of the present invention is
In the SiO ₂ —B ₂ O ₃ —R ₂ O type triangular composition diagram shown in FIG. 1, SiO ₂ is 89, B ₂ O ₃ is 10, and R ₂ O is 1 by weight%.
Is the fourth composition, 87 for SiO _{2 and} 1 for B ₂ O _3.
1.5, the composition in which R ₂ O is 1.5 is the fifth composition, Si
A composition in which O ₂ is 84.7, B ₂ O ₃ is 10.8, and R ₂ O is 4.5 is a ninth composition, SiO ₂ is 84, B ₂ O ₃ is 10,
A composition in which R ₂ O is 6 is a tenth composition, SiO ₂ is 90,
When the composition in which B ₂ O ₃ is 5 and R ₂ O is 5 is the 11th composition, a straight line connecting the points indicating the 4th composition and the point indicating the 5th composition and the 5th composition are shown. A straight line connecting the point and the point indicating the ninth composition, and a point indicating the ninth composition and the tenth point.
The straight line connecting the points indicating the composition, the straight line connecting the point indicating the tenth composition and the point indicating the eleventh composition, and the straight line connecting the point indicating the eleventh composition and the point indicating the fourth composition. It is the composition range indicated by the enclosed range (including the composition on the line).

The glass having the composition contained in this composition range has particularly high water resistance (that is, the amount of B ₂ O ₃ eluted is small) among the glasses contained in the above-mentioned first composition range. This second
The glass having a composition contained in the composition range (1) and the green sheet produced by using the glass are more preferable because there are almost no restrictions on the atmosphere for storage and handling.

Among the above composition ranges, SiO ₂ 8
7.0 wt% -B ₂ O ₃ 9.0 wt% -K ₂ O4.0% by weight of glass (8 Composition of) or composition in the vicinity thereof is excellent softening temperature, heat resistance, water resistance, most preferable.

The third composition range of the amorphous glass of the present invention is
A composition obtained by replacing the R ₂ O component of the glass having a composition contained in the second composition range with R ₂ O and Al ₂ O _{3 in} a molar amount of 90% or less of the molar amount of R ₂ O. It is a range. The glass of this composition is extremely preferable because the presence of Al ₂ O ₃ also suppresses the precipitation of cristobalite crystals from the glass due to the heat treatment. Furthermore, the addition of Al ₂ O ₃ has the effect of reducing the amount of B ₂ O ₃ eluted. However, if the addition of Al ₂ O ₃ exceeds 90% of the molar amount of R ₂ O contained in the glass, the softening temperature of the glass will be 1100 ° C.
Is exceeded, which is not preferable. Where R is N
Alkali metals such as a and K are shown, and K is most preferable from the viewpoint of water resistance.

The mechanism by which the precipitation of cristobalite crystals is suppressed by adding Al ₂ O ₃ is considered to be as follows.

The structure of the SiO ₂ —B ₂ O ₃ —R ₂ O type glass is as shown in FIG. 7A, the oxygen tetracoordinate of the Si atom, the oxygen tricoordinate of the B atom and the B atom. It is a disordered network structure of an oxygen tetracoordinate. Here, the oxygen tetracoordinate of the B atom attracts the R ion for charge compensation. When Al ₂ O ₃ is added to this ternary system, as shown in FIG. 7 (b), the oxygen tetracoordinator of the B atom becomes the oxygen tricoordinate of the B atom, and the Al ion attracting the R ion is attracted. An atomic oxygen tetracoordinate is formed. B ₂ O ₃ elution is better with the oxygen tricoordinate of B atom
It is more likely to occur than the B4 oxygen tetracoordinate. When the addition of Al ₂ O _{3 is} added, a slight increase in the amount of B ₂ O ₃ eluted is observed, which is considered to be because the oxygen tetracoordinate of B atom is changed to the oxygen tricoordinate of B atom. .

Next, a glass to which Al ₂ O ₃ is not added,
Consider the case where the glass to which Al ₂ O ₃ is added is heat-treated respectively. As described above, in the glass to which Al ₂ O ₃ is not added, the B atom is an oxygen tetracoordinate. As shown in FIG. 8A, the oxygen tetracoordinate of the B atom is B-
Since the O-bonding force and the R-ion attracting force are relatively small, it is considered that those bonds are easily broken at high temperature and non-bridging oxygen of Si is easily formed. Therefore, the viscosity at high temperature is lowered, and cristobalite crystals are likely to precipitate. On the other hand, in the glass to which Al ₂ O ₃ has been added, Al atoms are oxygen tetracoordinators. As shown in FIG. 8 (b),
Since the oxygen tetracoordinate of Al atom has a relatively large Al—O binding force and R ion attracting force, it is considered that those bonds are hard to be broken even at high temperature, and cristobalite crystals are hard to precipitate. However, if the amount of Al ₂ O ₃ added is too large, the side effect that the softening temperature of the glass becomes too high is unfavorable.

In the eighth composition, if Al ₂ O ₃ is added in a molar amount of 80% or more of the molar amount of K ₂ O, the precipitation of cristobalite crystals can be almost completely suppressed.
_{When the} amount of ₂ O ₃ added is 50% or more of the molar amount of K ₂ O, the amount of cristobalite crystal precipitation can be reduced to ⅕ or less. When the added amount of Al ₂ O ₃ is 80% of the molar amount of K ₂ O, the softening temperature is 1020 ° C., and when the added amount of Al ₂ O ₃ is higher than this, the softening temperature is also higher than 1020 ° C. . Since the softening temperature is most preferably around 1000 ° C., it is considered that the addition amount of Al ₂ O ₃ is particularly preferably 80% or less of the molar amount of K ₂ O. Therefore, A for the eighth composition
The amount of l ₂ O ₃ added is 50% or more and 80% or more of the molar amount of K ₂ O.
It is particularly desirable that the amount be below, and it is most preferable that the amount be at or near 70 mol%.

The fourth composition range of the amorphous glass of the present invention is
It is the range of the composition of the glass obtained by adding 1 to 4% by weight of ZnO to the glass of the first to third composition regions. The glass having this composition is preferable because it has a small B ₂ O ₃ elution amount and a low relative dielectric constant. When the added amount of ZnO is less than 1% by weight, the effect of addition cannot be obtained, and
If the addition amount of is larger than 4% by weight, crystal precipitation from the glass due to heat treatment tends to occur, which is not preferable.

The glass having the above-mentioned composition contains, for example, silicic acid anhydride (SiO ₂ ), boric acid (H ₃ BO ₃ ), and an alkali metal carbonate (R ₂ CO ₃ ), and if necessary, Alumina (Al ₂ O ₃ ) and / or zinc oxide (ZnO)
Was weighed so as to have a predetermined composition ratio, and subsequently, this mixed powder was put into a crucible after mixing in a ball mill, heated in a heating furnace at a temperature at which the mixed powder was sufficiently melted, and then rapidly cooled to produce an amorphous glass gob. It can be obtained by pulverizing so as to have a predetermined particle size.

F. Filler By the way, as the ceramic material for the ceramic wiring board, without using borosilicate glass alone, the mechanical strength is improved, the cristobalite crystal precipitation is suppressed, the coefficient of thermal expansion is matched with that of the LSI chip, and copper is used. A glass / filler composite material to which a filler is added for the purpose of shrinkage matching for co-sintering is used.

As such a filler, mullite,
Alumina, cordierite, and quartz are used alone or in a mixture thereof, and the amount of the filler added depends on the above purpose, relative permittivity, and densification / deformation / dimensional accuracy of the ceramic material by sintering. It is adjusted considering the configuration and process.

The filler added to the glass of the present invention is constituted as particles dispersed in the glass matrix phase after sintering, and has the function of (a) improving the mechanical strength of the glass ceramic composite, and (b) the glass ceramic. It has the effect of matching the thermal expansion coefficient of the composite with that of silicon, and the function of (c) suppressing the precipitation of cristobalite crystals by heat treatment from borosilicate glass. As described above, the glass ceramic composite preferably has high strength and low relative dielectric constant. Alumina as the filler is particularly the above (a),
The function (c), the mullite and the cordierite have the functions (a), (b), and (c) described above, and the quartz glass has a particularly low dielectric constant. In the present invention, each of these individual substances or a mixture of a plurality of types selected from them is added to the glass as a filler.

Next, the relationship between the amount of filler contained in the ceramic composition and pressure firing will be described. The amount of filler, the pressure applied during firing, the sintering temperature and the relative density (when 0% void, the relative density is 100%).
The relationship with is schematically shown in FIG.

In the present invention, it is desirable to apply pressure during firing. The amount of the filler added is in a range that allows the glass material to be densified while maintaining the maximum temperature during pressure firing. If the pressure applied during firing is set large, the amount of filler that can be added increases. However, as the amount of filler increases, the voids in the ceramic composed of glass and filler when densified will increase. The void of the ceramic body is preferably 5% or less, and in order to do so, depending on the particle diameters of the glass and the filler, the glass 50-1
It is preferable that the filler is 50 to 0% by volume with respect to 00% by volume. When the amount of filler added exceeds 50% by volume, glass for surrounding the filler even if the pressure and temperature are maximized within the range where the glass / copper wiring substrate can be produced (that is, within the range where the substrate is not destroyed). The voids in the glass-ceramic cannot be made 5% or less because of insufficient amount. In order to perform the sintering at a temperature of 1050 ° C. or lower, it is desirable that the filler content be 40% by volume or less of the whole ceramic.

<Binder Material> As the binder for the green sheet, it is desirable to use an aqueous material having a small amount of residual carbon as a binder residue after thermal decomposition so that the binder removal time can be shortened. Further, the binder material controls the mechanical properties of the green sheet, that is, the amount of strain when a large number of minute through holes are opened in the green sheet. A binder material that reduces the amount of strain is preferable.
From this point of view, it is desirable to use, as the binder, a material that is depolymerized by thermal decomposition, has a small amount of carbon residue during thermal decomposition, and has a small strain when the through hole is opened.

As such a binder material, it is preferable to use a polymer obtained by suspension polymerization using a water-soluble polymer as a dispersion stabilizer for polymerization. .

Specifically, (A) at least one of acrylic acid ester and methacrylic acid ester represented by the following general formula (Formula 1): 100 parts by weight,

[0070]

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(Wherein R ¹ is an alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group having 1 to 18 carbon atoms or an aryl group having 5 to 18 carbon atoms): 100 parts by weight, (B) Dispersion stabilizer: 1 to 9.5 parts by weight is dissolved in water or a mixed solution of water and a water-soluble organic solvent, and the component (A) is suspended (co) polymerized in the presence of a polymerization initiator. The organic binder for ceramic molding thus obtained is preferable. The organic binder used in the present invention has low hygroscopicity because it is not water-soluble but is water-based dispersion type particles, and thus the green sheet obtained by using it has good mechanical properties and dimensional stability.

The organic binder is used in a state of being dispersed in a solvent for preparing a binder, and the solid content concentration in that state is such that when the concentration is high, the particle size becomes large, and when the concentration is low, the amount of addition at the time of producing the green sheet is large. Since the workability such as adjustment and drying is lowered, it is preferably 20 to 50% by weight, more preferably about 30% by weight.

A. The monomer (A) component is the main component of the organic binder for ceramic molding, and the methacrylic acid ester is particularly preferable because it has good thermal decomposability. Among the methacrylic acid esters, particularly n-butyl methacrylate (hereinafter abbreviated as n-BMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-octyl methacrylate, methyl methacrylate, n-acrylate -Butyl (hereinafter abbreviated as n-BAA) and the like are preferable. Furthermore, among these, n-butyl methacrylate is particularly preferable from the viewpoints of thermal decomposability and hole position accuracy at the time of punching the green sheet.

B. Dispersion Stabilizer The component (B) is a water-soluble polymer used as a dispersion stabilizer for polymerization when the component (A) is polymerized in the presence of a polymerization initiator, and specifically, polyethylene oxide ( Hereinafter, abbreviated as PEO), polyvinyl-2-pyrrolidone, polyvinyl-2-pyrrolidone copolymer, poly (2-
Oxazoline) or the like is used. Of these, polyethylene oxide is particularly preferable from the viewpoint of thermal decomposability.

In the present invention, a binder of aqueous dispersion type particles is used. That is, the binder is in the form of particles when mixed with the ceramic powder in a ball mill, and the particulate binder is melted in the drying step. The molten binder bonds the individual ceramic particles, and the space occupied by the particulate binder becomes a space. Therefore, as the average particle diameter of the binder polymer as the binder for ceramic molding,
The size is equal to or smaller than the size of the ceramic particles used, 5 μm or less, preferably 3 μm or less.

In order to obtain such a particle size, it is preferable to use a water-soluble polymer (especially polyethylene oxide) having a viscosity average molecular weight of 10 to 1,000,000 as a dispersion stabilizer for polymerization. It is more preferable if it is up to 500,000. The amount of the water-soluble polymer (particularly polyethylene oxide) is preferably 1 to 9.5 parts by weight, and more preferably 6 to 8 parts by weight, based on 100 parts by weight of the monomer (A). When the amount of the component (B) which is a water-soluble polymer is less than 1 part by weight based on 100 parts by weight of the monomer of the component (A), the component (A) does not disperse and exceeds 9.5 parts by weight. In this case, it is not preferable in terms of thermal decomposability.

C. Polymerization Initiator Further, as the polymerization initiator, persulfates such as ammonium persulfate (hereinafter abbreviated as APS), peroxides, azo compounds and the like can be used, and are not particularly limited, but with respect to 100 parts by weight of the monomer. It is desirable that the total amount be 0.5 parts by weight or less.

D. As the solvent for preparing the solvent binder, water or a mixed liquid of water and one or more water-soluble organic solvent is used. As the water-soluble solvent, for example, either an alcohol represented by the following general formula (Formula 2) or an ethylene glycol derivative represented by the following general formula (Formula 3) can be used. As the alcohol, alcohols such as methanol, ethanol, propanol, and isopropanol (hereinafter abbreviated as IPA), ethylene glycol derivatives such as ethylene glycol methyl ether, and the like can be used. Of these organic solvents, IPA is particularly preferable.

[0079]

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(Wherein R ² is an alkyl group having 1 to 18 carbon atoms or a cyclic alkyl group having 1 to 18 carbon atoms)

[0081]

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(However, R ³ is hydrogen, having 1 to 18 carbon atoms.
Is an alkyl group having 1 to 18 carbon atoms, or an aryl group having 1 to 18 carbon atoms, and R ⁴ is hydrogen, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl group having 1 to 6 carbon atoms. A group or an aryl group having 5 to 6 carbon atoms,
n is 1 to 20) Further, the mixing ratio of these organic solvents and water is 100
It is desirable that the content of the water-soluble solvent be -50% by weight and the amount of the water-soluble solvent be 0-50% by weight.
More preferably, it is 50% by weight. In addition, the amount of the solvent for preparing the binder is 100 with respect to 100 parts by weight of the monomer.
The amount is preferably 400 to 400 parts by weight, more preferably around 250 parts by weight.

E. Plasticizer The green sheet binder preferably contains a plasticizer. It is preferable that the plasticizer has good compatibility with the binder solvent, does not azeotrope with water or the water-soluble organic solvent, and does not easily volatilize in the drying step during molding of the green sheet. Therefore, it is desirable to use at least one of the aromatic dicarboxylic acid esters represented by the following general formula (Formula 4) as the plasticizer.

[0084]

[Chemical 4]

(However, R ⁵ is an alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group having 1 to 18 carbon atoms, or an aryl group having 5 to 18 carbon atoms, and R ⁶ is 1 to 1 carbon atoms.
18 alkyl groups, C1-C18 cyclic alkyl groups,
Alternatively, it is an aryl group having 5 to 18 carbon atoms. Also, R
⁷ is a divalent aromatic group having 5 to 18 carbon atoms, and a phenylene group is particularly preferable. ) Specific examples of this plasticizer include phthalic acid esters such as diisodecyl phthalate (hereinafter abbreviated as DIDP), dibutyl phthalate (hereinafter abbreviated as DBP), di-2-ethylhexyl phthalate, and diisononyl phthalate. Of these, DIDP is preferable. The addition amount of the plasticizer is preferably 5 to 15 parts by weight, more preferably about 10 parts by weight, based on 100 parts by weight of the monomer.

F. Binder Preparation Method The binder can be prepared, for example, by the following procedure. First, 1 to 9.5 parts by weight of the component (B) is dissolved in a binder solvent, and about 0.15 parts by weight of a polymerization catalyst is added to the resulting solution. Four
The binder is obtained by adding 100 parts by weight of the component (A) and a plasticizer while carrying out vigorous stirring while heating at 0 to 90 ° C. to carry out a polymerization (or copolymerization) reaction.

The amount of component (A) to be added is preferably such that the solution concentration is 60% by weight or less in order to facilitate the polymerization reaction. In addition, since the binder determines the mechanical properties of the green sheet, that is, the amount of strain when a large number of minute through holes are opened in the green sheet, the amount of plasticizer also reduces this amount of strain, similar to the binder material. Therefore, it is desirable for high precision drilling.

<Green Sheet> A slurry is obtained by ball-mill mixing the ceramic powder of the present invention consisting of the amorphous glass and the filler, the above-mentioned binder, the dispersant, and the solvent for slurry. A green sheet is obtained by forming this slurry into a sheet and drying it.

A. Slurry solvent Incidentally, as the solvent for the slurry, from the viewpoint of dispersibility of the binder particles, the same solvent as in the binder preparation, that is, water,
Alternatively, it is desirable to use a mixed solvent of water and a water-soluble organic solvent, and it is particularly desirable to use a mixed solvent of water and isopropanol. Here, even when a mixed solvent of water and isopropanol is used, it is easy to flow sufficient air in the drying step at the time of forming the green sheet,
The solvent concentration in the air can be kept below the explosion limit.

B. Binder amount As the amount of binder, from the viewpoint of binder removal property, green sheet formability, and lamination pressure-bonding property, the ceramic powder 100 is used.
5 to 25 parts by weight is suitable with respect to parts by weight.

C. Dispersant Further, it is desirable to add a dispersant to disperse the ceramic powder. For example, polyacrylic acid ammonium salt or the like can be used, and the addition amount thereof is 0. The amount is preferably 5 parts by weight or less, particularly preferably 0.1 to 0.2 parts by weight.

D. Heat Treatment As previously mentioned, the binder of the present invention is mixed in the particulate state to bond between the ceramic particles. At this time, if the casting temperature is low, sufficient adhesive strength cannot be obtained. Therefore, in order to improve mechanical properties such as tensile strength and Young's modulus of the green sheet, a heat treatment may be appropriately performed during drying.

It is desirable that the temperature and time of this heat treatment are set under the condition that the binder particles are melted, and specifically, it is desirable that the temperature and time are about 80 to 120 ° C. and about 30 to 90 minutes. Under this heating condition, the binder particles can be melted and the ceramic particles can be sufficiently adhered to each other.

<Wiring Formation> In the present invention, since the green sheets can be punched with high positional accuracy, the ceramic substrates can be connected in the Z direction (thickness direction) with high positional accuracy when stacking the green sheets. It is possible to connect the wiring with a small diameter hole. Further, according to the present invention, since holes can be formed in the green sheet with high positional accuracy, a large number of via wirings can be connected at a short pitch, so that the wiring density can be increased as compared with the conventional one. Further, similarly, in the present invention, since it is possible to form a larger number of holes in the green sheet with higher positional accuracy than in the conventional case, the wiring width can be reduced accordingly, so that the XY direction (vertical and horizontal directions of the surface) can be improved. The wiring can also be densified.

By the way, for forming the wiring, a general wiring forming method can be applied. For example, when a copper wiring is formed by the screen printing method, Cu, Cu alloy,
Alternatively, a Cu paste containing a conductor such as Cu to which glass is added is printed on the surface of the green sheet with a screen plate and a screen printing machine on which a desired wiring pattern is formed to form a wiring pattern. In this case, the accuracy of wiring formation is determined by the pattern accuracy of the screen and the pattern accuracy at the time of screen printing, but this accuracy is higher than the positional accuracy at the time of drilling holes in the green sheet. In other words, the limit of high density wiring is roughly determined by the positional accuracy when drilling holes in the green sheet, and depends on the substrate size.
Before sintering, the pitch is about 0.15 mm.

<Firing> Higher dimensional accuracy when firing a ceramic wiring board can be achieved by applying pressure in the thickness direction of the ceramic wiring board during firing. That is, a frictional force or a restraining force is generated on the surface by applying pressure in the thickness direction during firing of ceramic molding. By optimally controlling this frictional force or restraint force, the average firing shrinkage can be reduced to almost zero, and at the same time, the shrinkage variation can be reduced to almost zero.

At this time, since the contraction suppressing force is generated by the frictional force acting between the pressed substrate and the pressing side, the contraction suppressing force increases as the distance from the constrained surface increases in the thickness direction. Becomes smaller, and conversely the amount of contraction becomes larger. That is, by optimizing the applied pressure so as to have a restraining force necessary for suppressing shrinkage of the substrate surface due to firing within a range in which the substrate is not crushed during firing, the lateral shape becomes concave.

Similarly, by applying a restraining force within a range capable of suppressing shrinkage due to firing of the substrate surface and controlling the amount of plastic deformation generated in the ceramic substrate material within an appropriate range, The side surface of the ceramic wiring board has a convex shape.

When the applied pressure is increased above the appropriate range, the substrate is largely crushed by the plastic deformation and the thickness of the substrate becomes less than a predetermined size, and at the same time, the internal wiring is deformed and the dimensional change of the elongation occurs in the substrate surface pattern. .

A green sheet was prepared using the glass material and binder of the present invention, copper wiring was formed on the surface of the green sheet, and pressure-sintering was performed in the plane direction (vertical and horizontal directions of the surface) and the thickness direction. The dimensional change rate is shown in FIG. If the frictional force is optimized by adjusting the pressing force, the dimensional change rate of the substrate surface pattern can be made almost zero in a certain pressing force range. At this time, the amount of change in the concave or convex side surface is preferably ½ or less of the thickness of the substrate after firing in consideration of the deformation of the internal wiring.

Here, as the pressing force and the friction coefficient,
It is not particularly limited because there are appropriate ranges depending on the material composition and firing conditions, but generally the pressing force is 100 g / cm ² or more, and the coefficient of friction is not particularly limited, and the substrate surface pattern It is only necessary to obtain the restraining force necessary to suppress the contraction of the.

To apply pressure to the molded body, for example, a large frictional force can be obtained on the contact surface, and between two plate-shaped pressure members having high dimensional stability in the firing temperature range of the ceramic molded body. Then, the ceramic compact is sandwiched and pressed. If the molded body is laminated while being sandwiched by the pressing member, it is possible to sinter two or more substrates at the same time.

If the thermal expansion coefficient of the pressing member is the same as that of the ceramic wiring board, the shrinkage rate becomes 0 when the pressure for completely restraining the shrinkage of the surface pattern is applied. If the thermal expansion coefficient of the pressure member is different from that of the ceramic wiring board, the temperature range between the room temperature and the room temperature at which the ceramic wiring board does not undergo plastic deformation in the cooling process of the firing process. Inside, a dimensional change occurs due to the difference in thermal expansion coefficient between the two. That is, when the thermal expansion coefficient of the pressing member is larger than that of the ceramic wiring board, a dimensional change occurs such that the surface pattern becomes smaller, and when the thermal expansion coefficient of the pressing member is smaller than that of the ceramic wiring board, A dimensional change occurs such that the surface pattern becomes large. From a different point of view, it is possible to adjust the dimensions of the ceramic wiring board by using materials with various thermal expansion coefficients for the pressure member, and control in the range of approximately -0.2% to + 0.8%. You can

It is more preferable that the applied pressure be optimized to the optimum pressure according to the temperature, rather than being kept constant throughout the firing process. The main factor that causes the dimensional change of the ceramic wiring board is the melting and thermal decomposition removal of the binder component in the green sheet and the Cu paste in the initial stage of firing, and the sintering shrinkage of the ceramic powder particles in the middle stage. This is due to the sintering shrinkage due to the liquid phase component accompanying the softening and melting of the glass component of the ceramic material in the latter stage. Since the shrinkage forces of sintering due to these causes are often different from each other, it is preferable to control the pressing force to be optimum at each stage.

Next, the relationship between pressure firing and binder removal will be described. It is necessary to remove the binder contained in the green sheet and the wiring conductor paste when forming a wiring pattern on the green sheet, stacking and pressing these, and firing the obtained laminated body to form a ceramic wiring board. is there. As a ceramic wiring board, a glass / copper wiring board will be described in detail here as an example.

Since copper is easily oxidized but is reduced in nitrogen, the binder is removed in a non-oxidizing atmosphere or a reducing atmosphere such as a mixed gas of nitrogen and steam, or a mixed gas of nitrogen, steam and hydrogen. Done. The carbon of the binder residue is removed by a thermodynamic reaction in steam. The subsequent sintering step is performed, for example, in a nitrogen atmosphere.

In order to shorten the binder removal time, it is desirable that the atmosphere gas is always spread within the substrate to be fired so that the carbon removal reaction rate is increased. Therefore, as the material of the pressing member for applying pressure to the substrate, a material having high air permeability is preferable.

Examples of such a material having high air permeability and having stable dimensions and strength equal to or higher than the pressing force as described above include, for example, porous ceramic plates and heat-resistant ceramic fiber materials obtained by molding. It is desirable to use a plate having a porosity of 50% or more, and more preferably 70% or more. When pressure is applied with a material of sufficient porosity with a porosity of 60% or more and sufficient atmospheric gas is supplied, air can be ventilated from the upper and lower surfaces as well as the side surface of the substrate. The binder can be removed in almost the same time as when it is placed on the base plate and fired.

Further, as described above, in order to shorten the carbon removal reaction in a short time, carbon is added to the glass used as the substrate material at a temperature as high as possible, preferably at 800 ° C. or higher. It is better to carry out at a temperature below the softening point of the glass so as not to be trapped and hinder the removal of carbon. In the present invention, since a high softening point glass material having a softening point of 850 to 1100 ° C. is used, the carbon removal reaction can be 800 ° C. or higher, and depending on the composition, 850 ° C. or higher. When the temperature is 850 ° C., it can be about 1/3 of the carbon removal time at 800 ° C., and the binder removal time can be further shortened.

In addition, this pressure firing is not limited to obtaining a ceramic wiring board with high dimensional accuracy, but can also absorb the difference in firing shrinkage between the ceramic material and the conductor material. The strict matching of firing shrinkage between the ceramic material and the conductor material, which is necessary in some cases, is not required. Further, the surface of the ceramic wiring board baked by pressure baking follows the surface of the pressure member,
It is as flat as the surface of the pressure member. As a result, the flatness of the substrate surface is significantly improved as compared with the case of normal pressureless firing. For example, the flatness of the pressure member surface is 20 μm.
Then, the surface of the substrate pressed against this surface is almost 2
It becomes 0 μm. This makes it possible to perform a thin film process (a process of forming a thin film wiring layer on the substrate surface) that requires strict flatness on the substrate surface without grinding the substrate surface.

Further, in the pressure firing, since the dimensional change does not occur during firing, it is not necessary to determine the shrinkage ratio for each substrate. Therefore, the screen design can be performed in the original size and the thin film wiring layer is formed on the substrate surface. In this case, there is almost no dimensional change as compared with the case of normal pressureless firing, the variation in shrinkage is significantly small, and the dimensional accuracy is good, which facilitates alignment and further reduces wiring density. It is possible to match with a high fine pattern. Further, in general pressureless sintering, there is about 20% shrinkage in the plane direction, but there is almost no shrinkage in pressure sintering. Therefore, it is possible to manufacture a large substrate with a smaller work size as compared with the case of general pressureless sintering.

<Thin Film Formation> Next, a method for forming a thin film wiring layer on at least one of the front and back surfaces of the ceramic multilayer wiring board (hereinafter, simply referred to as “substrate surface”) will be described.

First, after removing deposits on the surface of the substrate after sintering, the surface is washed and then a thin film process is performed. In addition, when the thick film wiring pattern on the substrate surface is not necessary or strict flatness is required,
After removing the deposits and before washing, if necessary,
Lapping is performed to flatten the substrate, and the surface is polished.

The thin film wiring layer is formed by the thin film process.
For example, it can be performed as follows.

First, a coating film formed by spin coating of a polyimide precursor varnish is dried and baked, and then 350 to 4
It is cured at a temperature of 00 ° C. to form a polyimide film. Then, after forming a desired resist pattern on the interlayer insulating film, the interlayer insulating film having a predetermined pattern is formed by etching with a hydrazine-ethylenediamine-based mixed solution or another alkaline mixed solution. The formation of this interlayer insulating film, using a photosensitive polyimide precursor composition,
It can also be formed by a photolithography method.

Thin film wiring is formed on the surface of the obtained interlayer insulating film. First, by sputtering on the entire surface of the interlayer insulating film, a chromium / copper / chrome laminated film or titanium /
A copper / titanium laminated film is formed. When it is necessary to secure the contact between the layers, sputter etching with argon gas is performed immediately before sputtering film formation. This laminated film is processed into a desired wiring pattern by using an etchant mainly containing an alkaline potassium permanganate aqueous solution or an alkaline potassium ferricyanide aqueous solution for chromium processing, and a phosphoric acid / nitric acid mixed solution etchant for copper processing. The processing of titanium is performed using an ammonia / hydrogen peroxide type etchant. As a result, a thin film wiring having a desired pattern can be obtained.

By repeating the above-described interlayer insulating film forming step and thin film wiring forming step a desired number of times, a predetermined number of thin film wiring layers are formed.

<Assembly of Electronic Circuit Device and Production of Electronic Computer> As an example of the assembly of the electronic circuit device, the assembly of the module for the electronic computer will be described.
The manufacturing process of the module for the electronic computer in the present invention is shown in FIG. In FIG. 22, (a) to (f)
Is a sintered body 4 of a ceramic multilayer wiring board, as in FIG.
1 shows a manufacturing process of No. 1, (a) is a ball mill process, (b) is a green sheet forming process, (c) is a hole forming process, (d) is a conductor printing process, and (e) is The lamination pressure-bonding step and (f) show the sintering step, respectively. Further, FIG. 22G shows a surface polishing step of the sintered body 41.
(H) is a thin film / thick film composite multilayer wiring board 71 which is a sintered body 41 having a thin film wiring layer 71 formed on the surface thereof, and (i) is a module 61 having a thin film / thick film composite multilayer wiring board 17.
(J) is an instruction processor 1 including a module 61
85 are shown respectively.

First, the thin film wiring layer 7 is formed on one side or both sides.
22 is formed on the ceramic multilayer wiring board (preferably a glass / copper multilayer wiring board) 17 (FIG. 22 (h)), the input / output pins 12, the semiconductor element or the chip carrier 11 with the semiconductor element sealed, and further for cooling The fins 15 and the water cooling jacket 16 are attached in this order to produce the module 61. The module 61 produced is shown in FIG.

It should be noted that, without directly connecting the input / output pins 12 and the like to the wiring pattern on the surface of the ceramic multilayer wiring board 17, a metal film layer having a necessary composition is formed as a sputtering film, and if necessary, plated to form a connection layer. May be formed, and the input / output pin 59 and the like may be attached via this connection layer.

For example, among these components, the input / output pin 12 is formed by forming a nickel / tungsten alloy film on the connection pad on the substrate surface by sputtering and then fixing a predetermined amount of brazing material to the head portion. The output pins are brazed to the back surface of the substrate by using a carbon positioning jig and reflowing in an atmosphere in which the metal layer is not oxidized. Similarly, via solder bumps of solder materials with different melting points,
The chip carrier 11 is subsequently soldered to the water cooling jacket 16 with solder having a different melting point.

Module 61 produced in this way
Are mounted on the multilayer printed circuit board 63 via the cable connector 18 and the water pipe 62 is connected,
Create the instruction processor 185. The produced instruction processor 185 is shown in FIG. If a plurality of the instruction processors 185 are used, a large-sized computer can be manufactured.

[0123]

【Example】

<Example 1> (1) as prepared _{SiO 2 -B 2 O 3 -R 2} O -based glass of the glass becomes a desired composition, silicic anhydride (SiO ₂₎ as a raw material, boric acid (H ₃ BO
₃ ) and potassium carbonate (K ₂ CO ₃ ) were weighed so as to have various composition ratios, and they were ball-mill mixed to obtain a mixed powder. Next, the mixed powder is put into a platinum crucible or a platinum-rhodium crucible, the crucible is put into an electric furnace, and the mixed powder in the crucible is heated at a temperature (melting temperature) for 1 hour, and then the crucible is put into an electric furnace. Then, the crucible was immersed in water and vitrified to obtain a glass lump of borosilicate glass. A part of the glass gob taken out from the crucible was used as a sample for measuring a thermal expansion coefficient, and another part was crushed to obtain a glass powder sample. For some of the prepared samples (samples having compositions 1 to 11), the respective composition ratios, the melting temperature of the glass prepared at the composition ratios, the B ₂ O ₃ elution amount, the softening temperature, and the thermal expansion coefficient. , Relative permittivity, and cristobalite crystal precipitation property are shown in Table 1. Moreover, each of these 1st-11th compositions is
In FIG. 1, each of these compositions is illustrated by a small circle having a center point. The numbers in the illustrated small circles indicate the composition numbers.

[0124]

[Table 1]

(2) Evaluation of Water Resistance of Glass Powder The water resistance of the obtained borosilicate glass was evaluated as follows. First, 1 g of a glass powder sample was placed in a beaker of Teflon (trade name of DuPont) having a volume of 300 ml containing 150 g of pure water, covered with a polyethylene film, and the Teflon beaker was placed in a constant temperature bath kept at 90 ° C. 8
I put in time. Next, the sample water in the Teflon beaker was taken out, centrifuged, and the supernatant liquid was filtered, and the obtained filtrate was used as an analysis liquid. The B atoms eluted in this analysis liquid are converted into ICP (Inductively Coated Plasma: Inductively Co).
upled Plasma) emission spectroscopy was used to determine the amount. Furthermore, the specific surface area of the glass is determined by the BET (Brunauer-Emmett-Teller) method, and from the detected value of B atom and the specific surface area of the glass,
The amount of B ₂ O ₃ eluted per unit surface area of the glass powder was calculated. The results are shown in Fig. 3. In addition, regarding the glasses having the first to eleventh compositions, the obtained B ₂ O ₃ elution amount is also shown in Table 1.
Note that FIG. 3 also includes experimental results for glasses having compositions other than those shown in Table 1.

In FIG. 3, line a indicates that the amount of B ₂ O ₃ eluted is 20.
mg / m ² isoelution amount curve, line b shows B ₂ O ₃ elution amount of 10
mg / m ² isoelution amount curve, line c shows B ₂ O ₃ elution amount of 6 m
g / m ² isoelution amount curve, line d shows B ₂ O ₃ elution amount of 4 mg
/ M ² isoelution amount curve, line e shows B ₂ O ₃ elution amount of 2 mg /
m ² isoelution amount curve, line f shows B ₂ O ₃ elution amount of 0.7 mg
/ M ² iso-elution amount curve, line g shows B ₂ O ₃ elution amount of 0.5 m
The iso-elution amount curve of g / m ² is shown. As shown in FIG. 3, the K ₂ O of about 3wt% or less of the glass composition of the glass component, B ₂ O ₃ elution amount decreases in accordance with K ₂ O component amount increases, K ₂ O of about 3wt In the glass composition exceeding%, the B ₂ O ₃ elution amount decreases as the B ₂ O ₃ component amount increases.

(3) Evaluation of Water Resistance of Green Sheets Green sheets were prepared using powder samples of SiO ₂ —B ₂ O ₃ —K ₂ O type glass having various compositions, and the green sheets were made to have a room temperature of 55 to 92%. It was left to stand in an atmosphere of relative humidity to examine the precipitation state of boric acid crystals.

When a glass composition having a B ₂ O ₃ elution amount of 20 mg / m ² (the third composition in Table 1, shown as a1 in FIG. 3) was used, it was allowed to stand for 1 month under 55% relative humidity. Then, no problematic precipitation of boric acid crystals was observed, but 75%
Precipitation of problematic boric acid crystals was observed after standing for 1 week at a relative humidity or higher.

On the other hand, a glass composition having a B ₂ O ₃ elution amount of 2 mg / m ² (the fourth composition in Table 1 (illustrated as e1 in FIG. 3), the fifth composition (illustrated as e2 in FIG. 3), 9th composition (illustrated as e3 in FIG. 3), 10th composition (FIG. 3)
7), and glass of five compositions having the composition shown as e5 in FIG. 3),
No problematic precipitation of boric acid crystals was observed even after standing for 2 months in an atmosphere of 5% to 92% relative humidity.

Therefore, the elution amount of B ₂ O ₃ was 20 mg / m 2.
^When a glass composition of ² or less is used, the restrictions on the atmosphere during storage and handling are loosened, and especially the amount of B ₂ O ₃ eluted is 2
The use of a glass composition of mg / m ² or less is preferable because there are almost no restrictions on the atmosphere during storage and handling. However, even a glass composition having a B ₂ O ₃ elution amount of 20 mg / m ² can be put to practical use and can be used in the present invention, although the atmosphere during storage and handling of the green sheet is limited. And other properties are preferred, they can be used in the present invention.

(4) Evaluation of Coefficient of Thermal Expansion With respect to the prepared borosilicate glass sample, a glass lump was processed into a diameter of about 4 mm and a length of about 15 mm, and a laser interference type thermal expansion meter was used in a temperature range of 0 ° C. to 200 ° C. The coefficient of thermal expansion was determined. Table 1 shows the calculated thermal expansion coefficients of the first to eleventh compositions. The glass having the first to eleventh compositions all have a low thermal expansion coefficient of 4.0 × 10 ⁻⁶ / ° C. or less, and by adding a filler, the thermal expansion coefficient can be easily matched with that of silicon. .

(5) Evaluation of Softening Temperature With respect to the glass powder sample, the softening temperature was measured by a usual differential thermal analysis. The measurement results of the first to eleventh compositions are shown in Table 1.
Shown in The softening temperature is preferably 850 to 1100 ° C. The softening temperatures of the glasses having the first to eleventh compositions are all included in this range, and from the results shown in Table 1,
It will be appreciated that these compositions are suitable for the present invention.

(6) Evaluation of Cristobalite Crystal Precipitation First, 1 g of a glass powder sample was subjected to an ordinary pressing method to obtain a diameter of 15 g.
mm disk shape, and heat it in an electric furnace at 800 ℃ 50
A heat treatment for holding for a time was performed to obtain a sintered body. The heat treatment conditions were set under the condition that the production conditions for the multi-layered substrate are assumed, and crystal precipitation from glass becomes severe. For the obtained sintered body, the amount of cristobalite crystals was measured by X-ray diffraction intensity. Table 1 shows the measurement results of the glasses having the first to eleventh compositions. For all compositions, the amount of precipitated cristobalite crystals was within the range for practical use, but in the sixth to eleventh compositions in which the amount of K ₂ O was large, the precipitation of cristobalite crystals was considerably observed. It was

(7) Evaluation of relative permittivity About 10 g of a glass powder sample was measured to have a diameter of 47 by an ordinary pressing method.
mm-shaped disc, which was heated to about 800 ° C in an electric furnace for 2
A heat treatment for holding for a time was performed to obtain a sintered body. The obtained sintered body is processed to a thickness of about 0.5 mm, and a Cr / Cu film is sputter-deposited as an electrode on both surfaces of the sintered body.
(Inductance capacitance resistance) The electrical capacitance was measured with a meter (measurement frequency: 1 MHz, input signal level: 1 Vrms) to determine the relative permittivity. First to first
Table 1 shows the measurement results of the glass having the composition of 1. The relative permittivities of the glasses having the first to eleventh compositions are all 5.0.
It is as low as possible and is preferable.

(8) Summary of Evaluation To summarize the above results, in the SiO ₂ —B ₂ O ₃ —R ₂ O system triangular composition diagram, the points indicating the first composition and the third composition Included in the range (including the composition on the line) surrounded by the line connecting the point indicating the composition of 10 and the point indicating the 11th composition, the point indicating the 4th composition and the point indicating the 1st composition in this order The glass having the composition described above has a softening temperature of 850 to 1100 ° C.
The water resistance is at a practical level, and the coefficient of thermal expansion is 4.
It was ^{0.times.10.sup.-6} / .degree. C. or less and could be matched with silicon by adding a filler. Further, the cristobalite crystal depositability and the relative dielectric constant are also practical.

On the other hand, a point indicating the fourth composition, a point indicating the fifth composition, a point indicating the ninth composition, a point indicating the tenth composition, a point indicating the eleventh composition, and the fourth composition. The glass having a composition contained in a range (including the composition on the line) surrounded by a line connecting the indicated points in this order has a particularly small B ₂ O ₃ elution amount of 2 mg / m ² or less. There is almost no limitation and it is particularly preferable.

<Example 2> Next, potassium carbonate (K ₂
CO ₃₎ with sodium carbonate (Na ₂ CO ₃₎ in place of, in the same manner as in Example 1, Si having various composition ratios of
The _{O 2 -B 2 O 3 -Na 2} O based glass was prepared. Various properties of the obtained glass sample were evaluated in the same manner as in Example 1. As with the K ₂ O-based glass of Example 1, the melting temperature, softening temperature and thermal expansion coefficient suitable for the purpose of the present invention were evaluated. ,
It had a relative permittivity. However, from the measurement results of water resistance and cristobalite crystal precipitation, it was confirmed that Na ₂ O
It was found that the system glass has the following features.

FIG. 19 shows the B ₂ O ₃ elution characteristics of SiO ₂ —B ₂ O ₃ —Na ₂ O based glass. In FIG. 19, the line a is B
₂ O ₃ elution amount of 20 mg / m ² isoelution amount curve, line b indicates B ₂
O ₃ elution amount of 10 mg / m ² isoelution amount curve, line c is B ₂
The isoelution amount curve of O ₃ elution amount of 6 mg / m ² , the line d is B ₂ O ₃
An elution amount curve with an elution amount of 4 mg / m ² is shown, and a line e shows an isoelution amount curve with a B ₂ O ₃ elution amount of 2 mg / m ² .

SiO ₂ -B ₂ O ₃ -K ₂ O based glass B ₂ O ₃
In the iso-elution curve (FIG. 3), the iso-elution curves are arranged substantially in parallel, whereas the B ₂ O ₃ iso-elution curve of SiO ₂ —B ₂ O ₃ —Na ₂ O-based glass (FIG. 19). Is disordered. It is considered that this is because the Na ₂ O-based glass has a large tendency to separate into two types of glass phases having different compositions, that is, a tendency to cause phase separation. Further, although the practical use of the Na ₂ O-based glass was not impaired, the amount of cristobalite crystals precipitated by the heat treatment was large, which was about twice that of the K ₂ O-based glass. Therefore, both Na ₂ O and K ₂ O can be used in the present invention, but the K ₂ O based glass, which has less tendency to phase-separate and has less precipitation of cristobalite crystals, is
It is considered to be more preferable.

Example 3 Next, SiO ₂ , B ₂ O ₃ , R ₂
A glass in which Al ₂ O ₃ is further included in addition to O is examined. In the present example, in the SiO ₂ —B ₂ O ₃ —R ₂ O system triangular composition diagram, a point indicating the first composition, a point indicating the third composition, a point indicating the tenth composition, and an eleventh composition. As an example of the composition contained in the range (including the composition on the line) surrounded by the line connecting the point indicating the above, the point indicating the fourth composition, and the point indicating the first composition in this order, SiO ₂ 86.6 wt %, B ₂
Composition of O ₃ 9.3 wt% and K ₂ O 4.1 wt% (approximately 8th
Was used to prepare a mixed powder of silicic acid anhydride, boric acid and potassium carbonate. Alumina (Al ₂ O ₃ ) powder was further added to this mixed powder so as to have the composition shown in Table 2, and the mixture was ball-milled.
A mixed powder having a composition of 16 was obtained. Using this mixed powder,
Glass was prepared in the same manner as in Example 1 and its characteristics were evaluated. Al ₂ O ₃ and R ₂ O in each composition
Table 2 shows the ratio (molar ratio) of (K ₂ O in this example) and the measurement results of the melting temperature, the thermal expansion coefficient, and the relative dielectric constant. As can be seen from the measurement results shown in Table 2, even if the amount of Al ₂ O ₃ added is increased, the thermal expansion coefficient and the relative permittivity hardly change, and they are within the preferable range.

[0141]

[Table 2]

Next, the effect of addition of Al ₂ O _{3 on} the amount of B ₂ O ₃ eluted will be examined. FIG. 4 shows the B ₂ O ₃ elution amounts of the glass having the eighth composition to which Al ₂ O ₃ was not added and the glasses having the 12th to 16th compositions. In FIG. 4, Al ₂
The amount of O ₃ added is standardized by the molar ratio with the amount of K ₂ O in the glass component. The numbers in the small circles indicate the glass composition numbers indicated by the small circles. It can be seen from FIG. 4 that the amount of B ₂ O ₃ eluted increases as the amount of Al ₂ O ₃ added increases. However, even if 90% Al ₂ O ₃ of the molar amount of K ₂ O was added, the elution amount of B ₂ O ₃ was as small as 1.6 mg / m ^2, and
It is considered that the increase in the amount of B ₂ O ₃ eluted by adding 1 ₂ O ₃ does not pose a problem.

Further, the effect of the addition of Al ₂ O _{3 on} the softening temperature will be examined. The softening temperatures of the eighth and twelfth to sixteenth compositions of glass are shown in FIG. In FIG. 5, as in FIG. 4, the amount of Al ₂ O ₃ added is normalized by the molar ratio with the amount of K ₂ O in the glass component. The numbers in the small circles indicate the glass composition numbers indicated by the small circles. From FIG. 5, it can be seen that when the added amount of Al ₂ O ₃ exceeds 90% of the molar amount of K ₂ O, the softening temperature of the glass having the composition exceeds 1100 ° C. Therefore, such a large amount of Al ₂ O ₃
Is not preferable.

Finally, the effect of the addition of Al ₂ O ₃ on the precipitation of cristobalite crystals will be examined. 8th,
FIG. 6 shows the amount of cristobalite precipitation (indicated by the diffraction intensity of cristobalite crystals) in the glass having the composition of 12 to 16. Also in FIG. 6, as in FIG. 4, Al
_The amount of ₂ O ₃ added is standardized by the molar ratio with the amount of K ₂ O in the glass component. The numbers in the small circles indicate the glass composition numbers indicated by the small circles. From FIG. 6, Al ₂ O ₃
X-ray diffraction intensity (that is, the amount of precipitated cristobalite crystals) as the amount of added cristobalite increased.
Can be seen to decrease. When the added amount of Al ₂ O ₃ is 80% or more of the molar amount of K ₂ O, cristobalite crystals do not precipitate even by the heat treatment.

Cristobalite crystals have about 2 as described above.
Since a crystal phase transition accompanied by a very large volume change occurs at 30 ° C., it causes cracking of the substrate and its precipitation is not preferable. However, in the reaction between the glass and the filler expected at the time of firing, if the filler material has the effect of suppressing the cristobalite crystals of borosilicate glass, even under the condition that the cristobalite crystals precipitate in the glass alone,
It will not precipitate. Therefore, when a substrate is prepared by using a composite of glass and a filler, even if the composition of glass is such that the cristobalite crystals are precipitated in the simple substance of glass, the cristobalite crystals are not precipitated in the composite composition with the filler. It can be said that there is no problem in applying the present invention. Therefore, even the glass having the eighth composition or the twelfth composition can be used in the present invention. However, even if the glass alone is used, if the precipitation of cristobalite crystals due to the heat treatment is suppressed, the range of selection of the filler material is widened and the manufacturing process can be stabilized.

From the above experimental results, it is found that it is desirable to prepare glass by adding 90% or less of Al ₂ O ₃ in molar ratio to R ₂ O. Further, if 50% or more of Al ₂ O ₃ is added to R ₂ O in a molar ratio, the precipitation of cristobalite crystals can be considerably suppressed, and 80%
It is understood from the above that the precipitation can be completely suppressed, which is very preferable.

Example 4 Next, SiO ₂ , B ₂ O ₃ , R ₂
The case of adding ZnO in addition to O and Al ₂ O ₃ (SiO ₂ —B ₂ O ₃ —R ₂ O—Al ₂ O ₃ —ZnO based glass) was examined. First, powders of anhydrous silicic acid, boric acid, potassium carbonate, sodium carbonate, alumina, and zinc oxide (ZnO), which were weighed so as to have the composition shown in Table 3, were ball-mill mixed, and compositions Nos. 17 to 23 shown in Table 3 were obtained. A mixed powder of Using this mixed powder, glass was prepared in the same manner as in Example 1 and its characteristics were evaluated. Table 3 shows the measurement results of the melting temperature, the B ₂ O ₃ elution amount, the softening temperature, the thermal expansion coefficient, the relative dielectric constant, and the cristobalite crystal precipitation property in each composition.

[0148]

[Table 3]

As shown in Table 3, all the glasses having the 17th to 23rd compositions have low B ₂ O ₃ elution amount, thermal expansion coefficient and relative dielectric constant, which are preferable. Also, the softening temperature is preferably 900 to 1060 ° C, which is preferable. Further, precipitation of cristobalite crystals is not observed, or even if it is observed, the amount is small, which is preferable.

Then, various amounts of ZnO powder were added to the raw material mixed powder having the second composition (composition ratio shown in Table 1) to prepare glass, and B ₂ O ₃ eluted from this glass was prepared. The amount was measured as in Example 1. ZnO addition amount and B ₂
The relationship with the amount of O ₃ eluted is shown in FIG. From FIG. 9, it is understood that the amount of B ₂ O ₃ eluted can be dramatically reduced by adding ZnO. Therefore, from this example, it is understood that it is preferable to add ZnO when the glass is prepared. In addition, as shown in Table 3, SiO ₂ −
_{B 2 O 3 -Na 2 O-} K 2 O-Al 2 O 3 -ZnO based glass amount of B ₂ O ₃ elution is small, is characterized in that the dielectric constant is low. If the added amount of ZnO is less than 1% by weight, the effect of the addition is not obtained, and the added amount of ZnO is 4% by weight.
If the amount is larger, there is a problem that crystal precipitation from the glass due to heat treatment tends to occur. Therefore, it can be seen from this example that the addition amount of ZnO is preferably 1% by weight or more and 4% by weight or less.

<Examples 5 to 21, Comparative Example 1> (1) Preparation of Sintered Body Next, the effect of mixing a filler in the glass composition was examined. First, in Examples 5 to 12 and Comparative Example 1, a glass powder having a 14th composition (shown in Table 2) was used, and in Examples 13 to 15, a 9th composition (shown in Table 1) was used.
Glass powder of Example 16 was used in Example 19 (Table 3).
Glass), a glass powder having a 23rd composition (shown in Table 3) in Examples 17 to 20, and a glass having a first composition (shown in Table 1) in Example 21. Powders were prepared. Filler powder was mixed with this glass powder at various ratios to obtain 18 kinds of ceramic composites shown in Table 4. The average particle diameter (diameter) of the glass powder was about 4 μm, and the average particle diameter (diameter) of the filler was about 3 μm. In addition, as a filler, Examples 1-11 and 13-1
5, 17 to 18 and Comparative Example 1, mullite (3Al ₂
O ₃ .2SiO ₂ ), mullite and alumina (Al ₂ O ₃ ) were used in Example 12, and alumina and cordierite (2MgO.2Al ₂ O ₃ .5Si) were used in Example 16.
O ₂ ), alumina is used in Examples 19 and 21, and alumina and quartz glass (SiO ₂ ) are used in Example 20.
₂ glass) was used.

100 parts by weight of the obtained ceramic composite, about 14 parts by weight of a water-soluble organic binder containing a modified acrylic resin as a main component, and about 75 parts by weight of water as a solvent,
A slurry was prepared by mixing 0.3 part by weight of an ammonium acrylate salt dispersant with a ball mill. Here, as the binder material, Hitaloid 27 is used as a water-soluble organic binder that has good hole-positioning accuracy and is preferable for environmental safety and hygiene.
13 (trade name: manufactured by Hitachi Chemical Co., Ltd.) was used.

[0153]

[Table 4]

Next, using the obtained slurry, a green sheet having a thickness of 0.2 mm and a width of 450 mm was prepared by a doctor blade method. The green sheet was cut into a square of 150 mm square or 50 mm square. Holes (through holes) having a diameter of 0.1 mm were punched at a pitch of 0.4 mm on a 150 mm square green sheet with a punch. A copper paste is embedded in the hole by a printing method to form a via hole, and the copper paste is printed on the surface of the green sheet to 0.08.
A wiring pattern with a width of mm formed by a normal method,
Laminate 4 to 50 layers and perform 10 at 130 ° C. and 20 MPa pressure.
After pressing for a minute, a green sheet laminate was obtained. Also,
The 50 mm square green sheet is a sample for measuring strength, relative permittivity, and residual carbon amount, and is laminated in 4 to 50 layers without punching or conductor printing, and at 130 ° C. and 20 MP.
It pressed for 10 minutes by the pressure of a, and the green sheet laminated body was obtained.

The obtained green sheet laminate was placed in an electric furnace capable of controlling the atmosphere, and the temperature inside the furnace was raised from room temperature to 700 to 880 ° C. under a steam-nitrogen-hydrogen gas atmosphere.
The temperature is raised at a heating rate of 00 ° C / hour, and the temperature is increased to 10 to 50
After holding for a period of time, binder removal firing was performed until the residual carbon became 200 ppm or less. Then, the temperature in the furnace was again raised to the sintering temperature shown in Table 4 at a temperature rising rate of 100 ° C./hour, and the temperature was maintained for 2 hours for densification sintering to obtain a ceramic sintered body. It was

The thermal expansion coefficient and the relative dielectric constant of the obtained ceramic sintered body (sintered body of a 50 mm square green sheet laminate) were measured by the same method as in Example 1. further,
The bending strength of this sintered body was processed according to JIS standard (R1601) so that the length was 38 mm, the width was 4 mm, and the thickness was 3 mm, and the bending strength was measured by a three-point bending test with a span of 30 mm. Table 4 shows the above measurement results.

The coefficient of thermal expansion of each of the ceramic sintered bodies of Examples 5 to 21 and Comparative Example 1 was 2.0 to 3.6 × 1.
0 ^-6 / ° C. and less, the thermal expansion coefficient of silicon (3.0 × 10
^The value was close to ⁻⁶ / ° C.). Further, the bending strength of each of the ceramic sintered bodies of Examples 5 to 21 and Comparative Example 1 was 150 MPa or more, and sufficient strength for practical use was obtained. Furthermore, in Examples 5 to 21, the sintering strength was 1050 ° C or lower. However, in Comparative Example 1, the sintering temperature reached 1100 ° C., which was an undesirable result. It is considered that this is because it was difficult to sinter because the amount of the filler was too large. Therefore, it is desirable that the amount of filler is not more than 40%.

Further, the residual carbon amount was measured by cutting out the central portion of the sintered body and quantifying the amount of carbon contained in the central portion of the sintered body. And 2 in each case of Comparative Example 1
It was less than 00 ppm, and favorable results were obtained. Furthermore, when the resistance of the copper conductor of the sintered body of the 150 mm square green sheet laminate was measured by the four terminal method, Example 5
21 and Comparative Example 1, the specific resistance of the copper conductor was a sufficiently small value of 3 μΩ · cm, which was a preferable value.

(2) Examination of binder removal temperature Next, the heat treatment temperature for binder removal will be examined. Using the green sheet of Example 9, binder removal was carried out at various temperatures, and the time required for the residual carbon content in the ceramic sintered body to reach 200 ppm or less (binder removal time) was measured. The results are shown in Fig. 10.
As can be seen from FIG. 10, the higher the heat treatment temperature, the shorter the holding time at that temperature, which is preferable.

(3) Examination of Filler Amount First, the amount of filler required for binder removal will be examined. A green sheet prepared by using various compositions of glass and various amounts of filler (mullite (3Al ₂ O ₃ .2SiO ₂ )) was debindered at 800 ° C or 850 ° C to obtain a ceramic sintered body. Of the green sheet that could reduce the residual carbon amount of
The softening temperature of the glass and the amount of filler were determined. The result is shown in FIG.

As can be seen from FIG. 11, as the softening temperature of the glass decreases, the amount of filler required for binder removal increases. Further, the higher the heat treatment temperature for binder removal, the larger the amount of filler required. This is because during the heat treatment for binder removal,
This is because it is necessary that the sintering of the glass particles does not proceed. Therefore, the lower the softening temperature of the glass or the higher the temperature of the binder is, the more filler is required to inhibit sintering.

Next, the amount of filler necessary for the densification sintering and the sintering temperature will be examined. First composition (softening temperature 1
100 ° C), second composition (softening temperature 1000 ° C), fifth
Of the four kinds of glass powders of composition No. 10 (softening temperature 950 ° C.) and composition No. 10 (softening temperature 850 ° C.) were added with various amounts of fillers (mullite) to prepare green sheets, and the green sheets were removed. Binder processing, further sintering,
The sintering temperature at which the relative density of the sintered body could be 98% or more was determined. FIG. 12 shows the relationship between the obtained sintering temperature and the amount of filler for each softening temperature of the glass used. FIG.
It can be seen from 2 that the heat treatment temperature (sintering temperature) required for the densification sintering increases as the amount of filler increases or the glass softening temperature increases.

The relationship between the amount of filler and the sintering temperature can be considered from the sintering shrinkage curve shown in FIG. For the sintering shrinkage curve, the green sheet laminate was put in a quartz glass reaction tube so that the shape and dimensions during heat treatment could be observed, and the shape at each temperature was photographed while heating at 100 ° C / min. , Was calculated by measuring the dimensions and calculating the relative density. In FIG. 13, a curve 131 is a sintering curve of the green sheet prepared using the glass of the fourteenth composition (without a filler), and curves 132 to 138 are the sintering curves of the green sheets of Examples 5 to 11, respectively. Shows.

From curve 131, it can be seen that the green sheet to which the filler has not been added rapidly sinters at around 800 ° C. and becomes densified. On the other hand, from the curves 132 to 138, in the green sheets of Examples 5 to 11 in which the filler of 10 to 40% by volume is added to the glass of the 14th composition, the relative density changes gently as the filler amount increases. It can be seen that sintering is less likely to occur. The sintering shrinkage curve shown in FIG. 13 is obtained by setting the holding time at each temperature as 0 hour, and it is considered that the densification proceeds further by increasing the holding time.

In order to sinter at a sintering temperature of 1050 ° C. or lower in a short time, it is necessary to reduce the amount of filler and use glass having a low glass softening temperature. On the other hand, as described above, if the amount of the filler is too small or the glass softening temperature is too low, the binder removal may not be completed. Further, even if the filler and the softening temperature are such that the binder can be removed, the sintering temperature becomes too high, which is not preferable in some cases. For example, as can be seen from FIG. 11, glass having a glass softening temperature of 820 ° C. is used,
When the amount of the filler is 50% by volume, the binder can be removed at 800 ° C., but in this case, the sintering temperature becomes 1050 ° C. or higher, which is not preferable, as inferred from FIG. . Therefore, when using the glass of the 14th composition, the upper limit of the amount of the filler densified and sintered at 1050 ° C. or lower can be considered to be 40% by volume. In addition,
The sinter shrinkage curve of the glass of the other composition is the sinter shrinkage curve (curve 131) of the glass of the 14th composition in the horizontal axis direction in FIG. 13 according to the softening temperature of the glass.
It can be obtained by moving in parallel.

Next, the relationship between the bending strength of the sintered body and the amount of filler will be examined. In addition to the sintered bodies obtained in Examples 5 to 11, a sintered body obtained by debindering and sintering the green sheet prepared from the glass of the fourteenth composition without adding a filler, and A green sheet prepared by adding 5 vol% mullite as a filler to glass having a composition of 14 was prepared by debindering and then sintering the green sheet. J
In accordance with IS standard (R1601), processed to have a length of 38 mm, a width of 4 mm, and a thickness of 3 mm, and a span 3
It was measured by a 0 mm 3-point bending test. FIG. 14 shows the relationship between the bending strength and the amount of filler of the obtained sintered body.

From FIG. 14, the amount of filler is from 5% by volume to 4%.
In the range of 0% by volume, practical strength (150 in this case)
Bending strength of MPa or more) is obtained, which is preferable. The bending strength is more preferably 200 MPa or more.

Example 22 A multilayer wiring board (the number of layers: 40) as shown in FIG. 15 was produced by the same method as in Example 5. The multilayer wiring board 17 manufactured according to the present embodiment is
The via hole 53 and the wiring 52, which have copper as a conductor, and the glass ceramic sintered body 158 are formed.

Next, as shown in FIG. 16, after the LSI (large scale integrated circuit) 11 and the I / O (input / output) pin 12 are attached by the brazing filler metals 13 and 14, as shown in FIG. The fins 15, the cooling jacket 16, and the connector 18 were attached, and an instruction processor 185 that was a module for an electronic computer was produced.

Further, using this instruction processor 185, as shown in FIG. 18, an electronic computer including a main storage device 181, an extended storage device 182, a system control device 183, an input / output processor 184, and an instruction processor 185 is manufactured. As a result, approximately twice as high-speed calculation was possible as compared with a conventional electronic computer including an instruction processor manufactured using a multilayer wiring board using mullite as a substrate material and tungsten as a conductor material.

The wiring board prepared in this embodiment can be widely applied to electronic circuit devices such as an electronic computer which requires particularly high speed and high density.

<Example 23> In Example 23, a glass / copper multilayer wiring board was produced using aqueous dispersion type particles as an organic binder. The manufacturing process will be described with reference to FIG.

(1) Synthesis of organic binder Purified water and isopropanol were mixed to prepare a binder preparation solvent (purified water: 70% by weight, IPA: 30% by weight). 7 parts by weight of polyethylene oxide, which is a dispersant, was dissolved in 250 parts by weight of this binder preparation solvent, and 0.15 parts by weight of ammonium persulfate was added as a polymerization initiator to the resulting solution at 40 to 90 ° C. 100 parts by weight of n-butyl methacrylate and 10.5 parts of diisodecyl phthalate as a plasticizer with vigorous stirring while heating to
Parts by weight, and further stirred for 6 to 8 hours, average particle diameter: 0.8 to 2.5 μm, average weight molecular weight: 50 to 65
An organic binder that is a polymer is obtained.

(2) Preparation of Slurry Next, a glass powder (average particle size: about 4 μm) having a fourteenth composition (shown in Table 2) was prepared.
By volume, 30% by volume of mullite powder having an average particle diameter of about 3 μm as a filler was mixed in advance to obtain a ceramic composite.

100 parts by weight of this ceramic composite, 0.13 parts by weight of a dispersant (ammonium polyacrylate), and 45 parts by weight of a solvent for preparing a slurry (mixed solution of 80% by weight of purified water and 20% by weight of isopropanol). And the alumina ball and the alumina lined ball mill 1 (see FIG. 2).
2 (a)) After premixing, the organic binder synthesized in (1) (those still dispersed in the binder preparation solvent)
Was added in an amount of 17 parts by weight in terms of binder solid content, and ball mill mixing was further continued to prepare a slurry in which glass powder, filler powder, and binder particles were uniformly mixed.

(3) Preparation of Green Sheet Subsequently, the slurry was stirred and the pressure was reduced to remove air bubbles in the slurry, the solvent was evaporated, and the viscosity was adjusted to 2000 to 3000 cps. 2 (FIG. 22 (b)) was applied onto a carrier film to form a green sheet 4 having a thickness of 0.2 mm and then dried at 120 ° C. for about 1 hour.

(4) Preparation of Ceramic Multilayer Wiring Substrate The green sheet 4 thus prepared was cut into a predetermined size and then fixed to a metal support frame. Successively, NC in which a plurality of carbide punch pins 5 can be independently driven
(Numerically controlled) Using a controlled punching device, the diameter of the green sheet fixed to the supporting frame is 50 to 70 mm.
Through holes 51 of μm were formed at a pitch of 0.3 mm (FIG. 22).
(C)). Subsequently, a Cu paste in which 50 parts by weight of Cu powder having an average particle diameter of 4 μm and 50 parts by weight of a vehicle are mixed is used to fill the through holes of the green sheet with the paste to form the via holes 53 by the screen printing method. A predetermined wiring pattern 52 was formed on the surface (FIG. 22 (d)).

Next, the green sheets 4 on which the wiring patterns 52 are formed are aligned with each other so that the displacement of the through-holes to be connected becomes small, and 50 sheets are stacked (see FIG. 22).
(E))), temperature: 130 ° C., pressure: 150 kg / cm
After pressure-bonding with ² and integration, the outer shape was cut into a predetermined size.
The dimensions of the obtained laminated body 41 were about 180 mm square and the thickness was about 10 mm.

Next, the firing process will be described. On the front and back of the laminate 41, porous plates 64 (a porosity of about 70% and a flatness of 30 μm) containing alumina fibers as main components are arranged, respectively, and an electric furnace 8 having a pressurizing mechanism and capable of controlling an atmosphere (FIG. 22). (F))) and the laminate 41 was pressed. Then, in a nitrogen atmosphere, the temperature is started to rise at a rate optimal for the binder to be set in advance, and when the temperature in the furnace 8 reaches a temperature at which dew condensation does not occur, the atmosphere in the furnace 8 is set to a mixed atmosphere of nitrogen and water vapor. (Steam partial pressure 0.3-0.
5 atm), and the binder was removed while maintaining the temperature at 850 ° C. for 10 to 20 hours.

The pressure applied to the laminate 41 at this time was about 1 to 3 kg / cm ² . This pressure is selected to be a relatively low pressure within the range in which the shrinkage in the planar direction can be almost zero in the binder removal process so as to secure the open porosity of the laminate 41 and not hinder the binder removal. It is a thing.

Subsequently, the steam was cut off, the atmosphere in the furnace was changed to a nitrogen atmosphere, and then the temperature of the laminated body 41 was again increased while being pressurized, and the temperature was maintained at the maximum temperature of 980 to 1040 ° C. for 1 to 3 hours. The porosity of the material was set to 5% or less so that the material was densified.

The pressure applied at this time is about 1 to 4 kg / c.
m ² to make it dense and to have almost no shrinkage in the plane direction
In addition, the control was performed so that the concave amount on the side surface became small.

Finally, the sintered body was cooled in a nitrogen atmosphere. In the cooling process, each was controlled so that the temperature and pressure profile were such that the residual stress was small. Through the above steps, a glass / copper multilayer wiring board was obtained.
The dimensional change in the firing step in this example was 0.15 ± 0.02% in the XY plane direction (vertical and horizontal directions of the substrate surface), and the shrinkage ratio in the thickness direction was about 45%.

Comparative Example 2 In Comparative Example 2, a commercially available Pyrex glass was used as the amorphous glass, and polyvinyl butyral was used as the organic binder to prepare a ceramic multilayer wiring board.

(1) Preparation of slurry 60% by volume of Pyrex glass powder having an average particle size of 4 μm
And 40% by volume of mullite powder having an average particle size of about 3 μm as a filler were mixed in advance to prepare a ceramic composite.

100 parts by weight of this ceramic composite, 6 parts by weight of polyvinyl butyral as an organic binder, 2 parts by weight of butylphthalyl butyl glycolate as a plasticizer, and an azeotropic composition consisting of trichloroethylene, tetrachloroethylene and butyl alcohol were used. A solvent was added and mixed well with an alumina ball and an alumina-lined ball mill 1 to prepare a slurry in which an amorphous glass powder and a filler powder were uniformly dispersed.

(2) Preparation of Green Sheet Next, the slurry was depressurized while stirring, and the viscosity was adjusted to 8000 to 13000 cps while deaerating the air bubbles, and then pressureless firing was performed using a doctor blade type casting device 2. Then, a green sheet 4 having a thickness of 0.14 mm was produced so as to have the same thickness as the substrate of Example 23.

(3) Preparation of Ceramic Multilayer Wiring Board After cutting the outer shape of the obtained green sheet 4 to have a predetermined size, the pitch was 0.3 mm after firing by the same method as in Example 23. A through hole 51 was formed in the through hole, a Cu paste was filled in the through hole 51 by a screen printing method, and a wiring pattern 52 was formed on the surface of the green sheet 4.

Next, 50 green sheets 4 having the wiring pattern 52 formed thereon were stacked in the same manner as in Example 23,
A laminated body 41 was produced by pressure-bonding at a temperature of 130 ° C. and a pressure of 150 kg / cm ² and integrating them. Obtained laminate 41
Was about 220 mm square and the thickness was about 7 mm.

Then, using the same electric furnace 8 as in Example 23, firing was performed without applying pressure. That is, in a nitrogen atmosphere, the temperature is started to rise at a rate optimal for a preset binder removal process, and when the temperature in the furnace reaches a temperature at which dew condensation does not occur, a mixed atmosphere of nitrogen and water vapor is formed, and the temperature is set to 20 to 30 at 800 ° C. The binder was removed while holding the time. Then, after steam is cut off and the atmosphere is changed to nitrogen, the temperature rise is started again, and the temperature is maintained at the maximum temperature of 970 to 1020 ° C. for 1 to 3 hours so that the glass ceramic material has a porosity of 5% or less and is densified. I tried to do it. The dimensional change in the firing step was 18 ± 0.29% in the XY plane direction, and the shrinkage ratio in the thickness direction was 20%.

(4) Evaluation of Substrate Here, when the process characteristics and substrate quality of Example 23 and this Comparative Example 2 are compared, the results are shown in Table 5.

[0192]

[Table 5]

From the evaluation results shown in Table 5, in Example 23, boric acid did not precipitate on the surface of the green sheet, the positional accuracy was good at the time of punching, and the dimensional change of the green sheet with time was small. It can be seen that a glass / copper multilayer wiring board with high dimensional accuracy, which is easy to densify the wiring, can be easily removed from the binder in a short time, and has no wiring defects even if high-density wiring is performed, is obtained.

In the twenty-third embodiment, as an example of high-density wiring, the punching of holes in the green sheet at a pitch of 0.3 mm has been described. However, by using thinner punch pins, holes at a pitch of about 0.15 mm are formed as a wiring board. Dawn is possible. Further, the specific numerical values described in Example 23 and Comparative Example 2 vary depending on the material composition, material configuration, substrate size and pattern structure, and process conditions, and are not particularly limited. Further, as for the glass material and the binder material, if the glass material and the binder material in the preferable material composition range described above, the process characteristics and the substrate quality substantially similar to those of the example 23 can be obtained.

<Examples 24 to 37> Examples 24 to 37
Then, a ceramic multilayer wiring board was produced in the same manner as in Example 23 except that the organic binder was different. Table 6 shows the organic binder monomer, dispersion stabilizer (polymerization dispersant), plasticizer, binder preparation solvent, and polymerization initiator synthesized in each example. In addition, in Table 6, "number"
Indicates an example number, and “initiator” indicates a polymerization initiator.

[0196]

[Table 6]

The wiring boards obtained in Examples 24 to 37 were the same good boards as in Example 23.

<Example 38> In Example 38, a module for an electronic computer was produced using the glass / copper multilayer wiring board obtained in Example 23. The manufacturing procedure will be described with reference to FIG.

First, after removing foreign matters attached to the front and back surfaces of the sintered body 158 of the glass / copper multilayer wiring board, the front and back surfaces are lapped by a thickness of not more than one sheet after firing the green sheet. It was removed (FIG. 22 (g)), and the front and back surfaces were further polished to a required surface roughness and then washed.

Subsequently, the coating film formed by spin coating of the polyimide precursor varnish is dried and baked on the surface of the substrate 158 and then cured at a temperature of 350 to 400 ° C. to form a polyimide insulating film for a protective film. did. Next, in order to form a thin film electrode pad for connecting the input / output pin 12 on the back surface of the substrate 158, sputter etching with argon gas is performed on the entire back surface of the substrate 158, and then chromium, copper, and chromium are continuously sputtered on the entire back surface in this order. Then, continuous wet etching was performed using the photoresist as a mask. In this etching, an alkaline potassium permanganate aqueous solution was used for chromium, and a phosphoric acid / nitric acid mixed solution was used for copper as etchants. After that, an interlayer insulating film 71 for a protective film was formed on the back surface of the substrate similarly to the front surface.

Subsequently, the thin film wiring 71 is formed on the surface side of the substrate 158.
Was formed by the following procedure (FIG. 22 (h)). First, the protective film on the surface of the substrate 158 is removed by an oxygen plasma asher, and then sputter etching with argon gas is performed on the entire surface of the substrate to form a matching pad, a wiring pattern and a sealing pattern, and then the substrate surface. Chrome on the entire surface,
Copper and chromium were successively sputter-deposited in this order, and continuous wet etching was performed using a photoresist as a mask. Next, an interlayer insulating film was formed and processed. That is,
The coating film formed by spin coating of the polyimide precursor varnish was dried and baked, then cured at a temperature of 350 to 400 ° C., and a resist pattern was formed on this surface and then etched to form a predetermined pattern. For processing, a hydrazine-ethylenediamine-based mixed solution was used. The above wiring pattern formation and interlayer insulating film formation were repeated to form the necessary thin film wiring layer 71. Thereby, the thin film / thick film composite multilayer wiring board 17 was obtained.

Next, a thin film electrode pad for solder connection was formed. First, on the surface of the substrate 17, chromium or titanium,
Subsequently, copper or nickel, a copper / nickel alloy, or a nickel / tungsten alloy was continuously sputter-deposited, a resist pattern was formed thereon, and etching was performed in order from the upper layer to form a thin film electrode pad for solder connection. Here, copper, nickel, copper / nickel alloy is processed by phosphoric acid / nitric acid mixed solution etchant, nickel / tungsten alloy is processed by hydrofluoric acid / nitric acid mixed solution etchant, and titanium is processed by ammonia / hydrogen peroxide type etchant. did. Next, the surface of this electrode pad was plated with gold. Similarly, the surface of the sealing pattern was also plated with gold.

Subsequently, the protective film on the back surface of the substrate 17 was removed by oxygen plasma asher, and the input / output pin 12 having the brazing material of Au--Sn 20 wt% eutectic alloy (melting point 280 ° C.) fixed to the head portion was replaced with carbon. Using a positioning jig made by
The back surface of the substrate 17 was brazed by reflowing at a temperature not lower than the melting point of the brazing material in an atmosphere in which the metal layer was not oxidized. Similarly, the chip carrier 11 was soldered through the solder bumps of solder materials having different melting points, subsequently the cooling fins 15 were combined, and the water cooling jacket 16 was further soldered using the solder having different melting points. In this way, the computer module 61 shown in FIG. 22 (i) was obtained.

A plurality of modules 61 obtained as described above are prepared and mounted on the multi-layer printed circuit board 63 via the connectors 18, respectively, to prepare an instruction processor 185. An electronic computer was made.

As a result, about 3 times as much calculation speed can be achieved as compared with the conventional method, for example, a large-scale computer manufactured using a mullite multilayer wiring board (wiring pitch 0.45 mm) made of mullite ceramics and a tungsten conductor. It was

The glass / copper multilayer wiring board obtained in Example 23 can be applied not only to the electronic computer manufactured in Example 38, but also to electronic circuit devices requiring high-density wiring and high-speed operation. .

[0207]

As described above, according to the present invention, binder removal is easy, densification and sintering are easy, and as a substrate characteristic, the coefficient of thermal expansion matches the coefficient of thermal expansion of silicon, and the bending strength is sufficiently large. A wiring board having a sufficiently small relative dielectric constant can be obtained. In particular, the composition of the present invention has a glass softening temperature of 8
Since it is as high as 50 to 1100 ° C., sintering shrinkage due to heat treatment for removing the binder hardly occurs, the binder can be removed by adding a small amount of the filler, and the densification and sintering can be performed in a short time firing. Further, the ceramic composition of the present invention and the glass contained in the composition have high water resistance, and it is difficult for boric acid crystals to be deposited on the green sheet. Moreover, the ceramic composition of the present invention can be converted from borosilicate glass by heat treatment. Cristobalite crystals do not precipitate, which is preferable. Therefore, according to the present invention, it is possible to significantly improve the productivity of the wiring board.

Further, according to the present invention, (a) a high softening point glass having good water resistance, (b) an aqueous dispersion type binder having good thermal decomposability and capable of forming a hole in a green sheet with high positional accuracy, (c) ) A glass / copper multilayer wiring board suitable for forming a thin film on the surface of the board with high wiring density and high dimensional accuracy by combining three elements of pressure sintering capable of sintering the board with high dimensional accuracy, and An electronic circuit device, a module for an electronic computer, and an electronic computer including the substrate can be manufactured.

For example, by using the high softening point glass (a) having good water resistance, boric acid precipitation on the surface of the green sheet can be avoided, and the binder can be removed at a high temperature. By using the binder of (b), a safe aqueous solvent can be used. Further, by performing the pressure sintering of (c), it becomes possible to form holes in the green sheet with high positional accuracy, and the dimensional change of the green sheet is suppressed, so that glass / copper with high dimensional accuracy can be suppressed. A multilayer wiring board can be manufactured, and high-density wiring is realized. Further, this pressure sintering reduces the binder removal time. Accordingly, even if the high softening point glass of (a) is used, it is possible to avoid that the binder removal takes an excessive time.

Further, in the present invention, environmental measures can be taken by using the aqueous dispersion type binder, and the binder removal time can be shortened by using the high softening point glass, so that the substrate can be manufactured at low cost.

[Brief description of drawings]

FIG. 1 shows SiO representing the composition range of the amorphous glass of the present invention.
₂ is a -B ₂ O ₃ -R ₂ O3 component triangular composition diagram.

FIG. 2 is an explanatory diagram showing a manufacturing process of a multilayer wiring board.

FIG. 3 SiO ₂ —B ₂ O ₃ showing a B ₂ O ₃ isoelution curve
FIG. 3 is a triangular composition diagram of a K ₂ O 3 component system.

FIG. 4 is a graph showing a relationship between a B ₂ O ₃ elution amount of SiO ₂ —B ₂ O ₃ —K ₂ O—Al ₂ O ₃ based glass and a molar ratio of Al ₂ O ₃ / K ₂ O.

FIG. 5 is a graph showing the relationship between the softening temperature of SiO ₂ —B ₂ O ₃ —K ₂ O—Al ₂ O ₃ based glass and the Al ₂ O ₃ / K ₂ O molar ratio.

FIG. 6 is a graph showing the relationship between the cristobalite precipitation property of SiO ₂ —B ₂ O ₃ —K ₂ O—Al ₂ O ₃ based glass and the Al ₂ O ₃ / K ₂ O molar ratio.

FIG. 7A is an explanatory view showing a structural model of SiO ₂ —B ₂ O ₃ —R ₂ O based glass. 7 (b) shows Si
The _{O 2 -B 2 O 3 -R 2} O -based glass is an explanatory diagram showing the structural change of adding the Al ₂ O ₃ component.

FIG. 8 (a) is an explanatory view showing a structural change in the case of heating SiO ₂ —B ₂ O ₃ —R ₂ O based glass to a high temperature. FIG. 8B is an explanatory view showing a structural change when the SiO ₂ —B ₂ O ₃ —R ₂ O—Al ₂ O ₃ based glass is heated to a high temperature.

9 SiO ₂ -B ₂ O ₃ of -ZnO type glass B ₂ O ₃
It is a graph which shows the relationship between the elution amount and the ZnO addition amount.

FIG. 10 is a graph showing the relationship between binder removal temperature and binder removal time.

FIG. 11 is a graph showing the relationship between the softening temperature of glass and the amount of filler required for binder removal.

FIG. 12 is a graph showing the relationship between the densification and sintering temperature of a glass-filler composition, the amount of filler, and the glass softening temperature.

FIG. 13 is a graph showing a sintering shrinkage curve of a glass-filler composition.

FIG. 14 is a graph showing the relationship between the bending strength of a glass-filler sintered body and the amount of filler.

FIG. 15 is a sectional view of a multilayer wiring board of example 22.

FIG. 16 is a cross-sectional view of a multilayer wiring board on which an LSI and I / O pins of Example 22 are mounted.

FIG. 17 is a partial cross-sectional view of the instruction processor module of the twenty-second embodiment.

FIG. 18 is a system configuration diagram of an electronic computer of Example 22.

FIG. 19 shows SiO ₂ —B ₂ O showing a B ₂ O ₃ isoelution curve.
FIG. 3 is a triangular composition diagram of a _3- Na ₂ O 3 component system.

FIG. 20 is a graph showing the relationship between the applied pressure and the dimensional changes in the plane direction and the thickness direction of the substrate in pressure sintering.

FIG. 21 is a graph showing the relationship among the amount of filler, the applied pressure, the sintering temperature, and the relative density in pressure sintering.

FIG. 22 is an explanatory diagram showing the manufacturing process of the computer module.

FIG. 23 is a partial cross-sectional perspective view showing the structure of a computer module.

FIG. 24 is a perspective view showing the structure of an instruction processor.

[Explanation of symbols]

1 ... Ball mill device, 2 ... Slurry, 3 ... Casting machine, 4 ... Green sheet, 5 ... Punch, 6 ... Squeegee, 7 ... Paste, 8 ... Heating furnace, 9 ... Via hole, 1
0 ... Wiring, 11 ... LSI, 12 ... I / O (input / output) pins, 13 and 14 ... Connection brazing material, 15 ... Micro fin, 16 ... Water cooling jacket, 17 ... Multilayer wiring board, 18
... connector, 41 ... laminated body, 51 ... through hole, 52 ... wiring, 53 ... via hole, 61 ... module, 62 ... water pipe, 63 ... multilayer printed board, 71 ... thin film wiring layer, 1
58 ... Glass ceramic sintered body, 181 ... Main memory device,
182 ... Extended storage device, 183 ... System control device, 1
84 ... I / O processor, 185 ... Instruction processor.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Heiyoshi Tanei 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa Inside the Hitachi, Ltd. Institute of Industrial Science (72) Inventor Shoichi Iwanaga 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa Hitachi Ltd., Production Engineering Laboratory (72) Inventor, Fusuji Shoko, 292 Yoshida-cho, Totsuka-ku, Yokohama, Kanagawa Prefecture, Ltd. Production Engineering Laboratory, Hitachi (72) Inventor, Nobuhito Katsumura Yoshida, Totsuka-ku, Yokohama, Kanagawa Prefecture 292, Machi, Ltd., Production Engineering Laboratory, Hitachi, Ltd. (72) Ryohei Sato, Ryohei Sato, 292, Yoshida-cho, Totsuka-ku, Yokohama, Kanagawa Prefecture, Ltd., Production Engineering Laboratory, Hitachi, Ltd. (72) Futami Kobayashi, Kanagawa Prefecture 1 Horiyamashita, Hadano City General Manager Computer Division, Hiritsu Manufacturing Co., Ltd. (72) Inventor Tagami Ichigo Horiyamashita, Hadano, Kanagawa, Japan 1st, General Computer Division, Hiritsu Mfg. Co., Ltd. (72) Norio Sengoku 1st, Horiyamashita, Hadano, Hadano, Kanagawa Pref., General Computer Div., Hitate, Kunihiro Yagi Kanagawa Horiyamashita No. 1, Hadano-shi, Hyogo, Ltd. General-purpose computer division, Hiritsu Manufacturing Co., Ltd. (72) Masato Nakamura, 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa Hitachi, Ltd. Production Engineering Research Laboratory (72) Inventor Kosaku Morita Kanagawa Production Engineering Laboratory, Hitachi, Ltd., 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Japan (72) Inventor Takeshi Fujita, 292 Yoshida-cho, Totsuka-ku, Yokohama, Kanagawa

Claims (46)

[Claims] 1. A slurry preparation step of preparing a slurry by mixing amorphous glass, a filler, an organic binder, and a solvent for preparing a slurry; and processing the slurry into a sheet to prepare a green sheet. Green sheet preparation step, conductor forming step of forming via holes and / or wiring in the green sheet, heating the green sheet to 700 to 880 ° C. to remove the binder, and heating to 900 to 1050 ° C. to sinter And a heating step in this order, and the amorphous glass is a glass having a softening temperature of 850 to 1100 ° C. 2. The slurry preparation step according to claim 1, wherein the amorphous glass, the filler, the organic binder, and the solvent for preparing the slurry are mixed to prepare a slurry, and the slurry is processed into a sheet shape. A green sheet preparing step of preparing a green sheet, a conductor forming step of forming via holes and / or wirings in the green sheet, and heating the green sheet to a first heating temperature to remove the binder, A heating step of heating to a second heating temperature higher than the heating temperature and sintering, in this order, the amorphous glass has a SiO ₂ component, a B ₂ O ₃ component, and an R ₂ O component (however, R represents an alkali metal), and the total weight of the SiO ₂ component, the B ₂ O ₃ component, and the R ₂ O component is 100%, and the SiO ₂ component is 88 wt% and the B ₂ O ₃ component is 12 wt%. And The composition first composition, SiO ₂ component is 82 wt%, B ₂ O ₃ composition component is 18 wt% third composition, SiO ₂ component is 84 wt%, B ₂ O ₃ component is 10 wt% ,
The composition having 6% by weight of the R ₂ O component is the 10th composition, 90% by weight of the SiO ₂ component, 5% by weight of the B ₂ O ₃ component, and R ₂
The 11th composition is a composition in which the O component is 5% by weight, the SiO ₂ component is 89% by weight, the B ₂ O ₃ component is 10% by weight,
When the composition in which the R ₂ O component is 1 wt% is the fourth composition, in the SiO ₂ —B ₂ O ₃ —R ₂ O system triangular composition diagram, the points indicating the first composition and the third composition are Point, third composition and tenth composition, tenth composition and eleventh composition, eleventh composition and fourth composition , A point indicating the fourth composition and a point indicating the first composition, respectively, having a composition indicated by a point within a region (including on the line) surrounded by a line connecting the points. 3. The method for manufacturing a wiring board according to claim 2, wherein the first heating temperature is 700 to 880 ° C. and the second heating temperature is 900 to 1050 ° C. 4. The method of claim 2, the amorphous glass, SiO ₂ component, B ₂ O ₃ component, and the total weight of the R ₂ O component and 100%, SiO ₂ component is 87 wt%, B ₂ The fifth composition has a composition in which the O ₃ component is 11.5% by weight and the R ₂ O component is 1.5% by weight, the SiO ₂ component is 84.7% by weight, and the B ₂ O ₃ component is 10.8% by weight.
In the case where the composition containing 9% by weight and 4.5% by weight of R ₂ O is the 9th composition, a point showing the 4th composition in the SiO ₂ —B ₂ O ₃ —R ₂ O system triangular composition diagram And a point indicating the fifth composition, a point indicating the fifth composition, a point indicating the ninth composition, a point indicating the ninth composition, a point indicating the tenth composition, and a point indicating the tenth composition. And the point indicating the eleventh composition, and the first composition
1. A method for manufacturing a wiring board, which has a composition indicated by a point within a region (including a line) surrounded by a line connecting the point indicating the composition No. 1 and the point indicating the fourth composition. 5. The method for manufacturing a wiring board according to claim 2, wherein R is potassium. 6. The amorphous glass according to claim 2, wherein the R ₂ O component is substituted for the R ₂ O component.
Component and 90% by mole or less of the molar amount of the R ₂ O component, Al ₂ O
_A method of manufacturing a wiring board, which comprises _three components. 7. The amorphous glass according to claim 2, wherein the amorphous glass is 1 to 4 with respect to the entire amorphous glass.
A method of manufacturing a wiring board, further comprising a ZnO component in a weight percentage. 8. The organic binder according to claim 1 or 2, wherein (A) at least one type of acrylic acid ester and methacrylic acid ester represented by the following general formula (Formula 1): 100 parts by weight, Chemical 1] (However, R ¹ is an alkyl group having 1 to 18 carbon atoms,
Cyclic alkyl group having 1 to 18 carbon atoms or 5 carbon atoms
.About.18 aryl groups): 100 parts by weight and (B) dispersion stabilizer: 1 to 9.5 parts by weight are dissolved in a binder preparation solvent, and the above component (A) is added in the presence of a polymerization initiator. A method for producing a wiring board, which is a polymer obtained by suspension polymerization or suspension copolymerization. 9. The method of manufacturing a wiring board according to claim 8, wherein the component (A) is methacrylic acid ester. 10. The method of manufacturing a wiring board according to claim 9, wherein the component (A) is n-butyl methacrylate. 11. The method for manufacturing a wiring board according to claim 8, wherein the dispersion stabilizer is a water-soluble organic polymer having a viscosity average molecular weight of 100,000 to 1,000,000. 12. The component (B) according to claim 11, wherein the component (B) is at least one selected from polyethylene oxide, polyvinyl-2-pyrrolidone, polyvinyl-2-pyrrolidone copolymer, and poly (2-oxazoline). A method for manufacturing a wiring board, which is a polymer. 13. The method of manufacturing a wiring board according to claim 1, wherein the organic binder is aqueous dispersion type particles. 14. The method for manufacturing a wiring board according to claim 13, wherein the organic binder has an average particle diameter of 5 μm or less. 15. The method for manufacturing a wiring board according to claim 8, wherein the polymerization initiator is at least one compound selected from persulfates, peroxides, and azo compounds. 16. The method for manufacturing a wiring board according to claim 8, wherein the binder preparation solvent is water or a mixed liquid of water and a water-soluble organic solvent. 17. The water-soluble organic solvent according to claim 16, is selected from an alcohol represented by the following general formula (Formula 2) and an ethylene glycol derivative represented by the following general formula (Formula 3). A method for manufacturing a wiring board, wherein the wiring board is at least one compound. Embedded image (However, R ² is an alkyl group having 1 to 18 carbon atoms or a cyclic alkyl group having 1 to 18 carbon atoms) embedded image (However, R ³ is hydrogen, an alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group having 1 to 18 carbon atoms, or an aryl group having 5 to 18 carbon atoms, and R ⁴ is hydrogen and 1 carbon atoms.
To C6 alkyl group, C1 to C6 cyclic alkyl group, or C5 to C6 aryl group, and n is 1 to 20.
Is) 18. The method of manufacturing a wiring board according to claim 17, wherein the water-soluble organic solvent is at least one compound selected from methanol, ethanol, propanol, isopropanol, and ethylene glycol methyl ether. 19. The method of manufacturing a wiring board according to claim 16, wherein the binder preparation solvent comprises 100 to 50% by weight of water and 0 to 50% by weight of a water-soluble solvent. 20. The method for manufacturing a wiring board according to claim 8, wherein the organic binder further contains a plasticizer. 21. The method of manufacturing a wiring board according to claim 20, wherein the plasticizer is at least one of aromatic dicarboxylic acid esters represented by the following general formula (Formula 4). [Chemical 4] (However, R ⁵ is an alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group having 1 to 18 carbon atoms, or 5 to 18 carbon atoms.
R ⁶ is an alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group having 1 to 18 carbon atoms, or an aryl group having 5 to 18 carbon atoms. Also, R ⁷ has 5 carbon atoms
To 18 divalent aromatic groups. ) 22. The method for manufacturing a wiring board according to claim 1, wherein the slurry preparation solvent is water or a mixed liquid of water and a water-soluble organic solvent. 23. The method for manufacturing a wiring board according to claim 8, wherein the slurry preparation solvent and the binder preparation solvent are the same solvent. 24. The method of manufacturing a wiring board according to claim 1, wherein the heating at 900 to 1050 ° C. in the heating step is performed while applying a pressure in the thickness direction to the green sheet. . 25. The method for manufacturing a wiring board according to claim 24, wherein the pressure is applied through a flat plate having a porosity of 50% or more. 26. The method of manufacturing a wiring board according to claim 1, wherein the filler is at least one selected from alumina, mullite, cordierite, and quartz glass. 27. The total volume of the amorphous glass and the filler according to claim 1 or 2,
%, The amorphous glass is 60 to 95% by volume, and the filler is 40 to 5% by volume. 28. The green sheet laminate according to claim 1, wherein a plurality of green sheets having the via holes and / or wirings are laminated and adhered between the conductor forming step and the heating step. A method for manufacturing a wiring board, further comprising a stacking step for forming the green sheet, wherein the green sheet heated in the heating step is the green sheet stacked body stacked in the stacking step. 29. The method of manufacturing a wiring board according to claim 1, wherein the conductor is copper. 30. SiO ₂ component, B ₂ O ₃ component, and R ₂ O
The first composition is a composition in which the total weight of the components is 100%, the SiO ₂ component is 88% by weight, the B ₂ O ₃ component is 12% by weight, the SiO ₂ component is 82% by weight, and the B ₂ O ₃ component is 18% by weight. The third composition is the composition which is wt%, the SiO ₂ component is 84 wt%, the B ₂ O ₃ component is 10 wt%,
The composition having 6% by weight of the R ₂ O component is the 10th composition, 90% by weight of the SiO ₂ component, 5% by weight of the B ₂ O ₃ component, and R ₂
The 11th composition is a composition in which the O component is 5% by weight, the SiO ₂ component is 89% by weight, the B ₂ O ₃ component is 10% by weight,
When the composition in which the R ₂ O component is 1 wt% is the fourth composition, in the SiO ₂ —B ₂ O ₃ —R ₂ O system triangular composition diagram, the points indicating the first composition and the third composition are Point, third composition and tenth composition, tenth composition and eleventh composition, eleventh composition and fourth composition , A point indicating the fourth composition and a point indicating the first composition, the R ₂ O component is an alkali metal oxide component, and the R ₂ O component is an alkali metal oxide component. And 90% by mole or less of the molar amount of the alkali metal oxide component Al ₂
An amorphous glass characterized by comprising an O ₃ component. 31. The amorphous glass according to claim 30, wherein R is potassium. 32. The amorphous glass according to claim 30, further comprising 1 to 4% by weight of ZnO component with respect to the entire amorphous glass. 33. A ceramic composition for a wiring board, which comprises amorphous glass and a filler, wherein when the total volume of the ceramic composition is 100%, then 6
Consisting of 0 to 95% by volume of amorphous glass and 40 to 5% by volume of filler, and containing SiO ₂ component, B ₂ O ₃ component, R ₂ O component (where R represents an alkali metal), The total weight of the SiO ₂ component, the B ₂ O ₃ component, and the R ₂ O component is 100%, and the composition in which the SiO ₂ component is 88 wt% and the B ₂ O ₃ component is 12 wt% is the first composition, SiO _{The second} composition is 82% by weight, the B ₂ O ₃ component is 18% by weight, and the third composition is 84% by weight, the SiO ₂ component is 84% by weight, and the B ₂ O ₃ component is 10% by weight.
The composition having 6% by weight of the R ₂ O component is the 10th composition, 90% by weight of the SiO ₂ component, 5% by weight of the B ₂ O ₃ component, and R ₂
The 11th composition is a composition in which the O component is 5% by weight, the SiO ₂ component is 89% by weight, the B ₂ O ₃ component is 10% by weight,
When the composition in which the R ₂ O component is 1 wt% is the fourth composition, in the SiO ₂ —B ₂ O ₃ —R ₂ O system triangular composition diagram, the points indicating the first composition and the third composition are Point, third composition and tenth composition, tenth composition and eleventh composition, eleventh composition and fourth composition , A point indicating the fourth composition and a point indicating the first composition, the ceramic composition for a wiring board having a composition indicated by a point inside (including on the line) surrounded by a line connecting the points. In 34. The method of claim 33, said amorphous glass, SiO ₂ component, B ₂ O ₃ component, and the total weight of the R ₂ O component and 100%, SiO ₂ component is 87 wt%, B ₂ The fifth composition has a composition in which the O ₃ component is 11.5% by weight and the R ₂ O component is 1.5% by weight, the SiO ₂ component is 84.7% by weight, and the B ₂ O ₃ component is 10.8% by weight.
In the case where the composition containing 9% by weight and 4.5% by weight of R ₂ O is the 9th composition, a point showing the 4th composition in the SiO ₂ —B ₂ O ₃ —R ₂ O system triangular composition diagram And a point indicating the fifth composition, a point indicating the fifth composition, a point indicating the ninth composition, a point indicating the ninth composition, a point indicating the tenth composition, and a point indicating the tenth composition. And the point indicating the eleventh composition, and the first composition
1. A ceramic composition for a wiring board, which has a composition indicated by a point within a region (including a line) surrounded by a line connecting each of the points indicating the composition No. 1 and the point indicating the fourth composition. 35. The ceramic composition for a wiring board as claimed in claim 33, wherein R is potassium. 36. The amorphous glass according to claim 33, wherein R ₂ O is used in place of the R ₂ O component.
Component and 90% by mole or less of the molar amount of the R ₂ O component, Al ₂ O
_A ceramic composition for a wiring board, which comprises _three components. 37. The amorphous glass according to claim 33, wherein the amount of the amorphous glass is 1 to 4 with respect to the entire amorphous glass.
A ceramic composition for a wiring board, which further comprises a ZnO component by weight. 38. A wiring board ceramic composition comprising amorphous glass and a filler, wherein the volume of the amorphous glass is 60 to 95% when the total volume of the ceramic composition is 100%. The volume of the filler is 40 to 5%, and the amorphous glass has a softening temperature of 850 to 1100 ° C. 39. The ceramic composition for a wiring board as defined in claim 33, wherein the filler is at least one selected from alumina, mullite, cordierite, and quartz glass. 40. A wiring board comprising a via and a wiring made of a conductor and a base material made of a ceramic, wherein the ceramic has a total volume of the ceramic of 60 to 95.
It is a sintered body obtained by sintering volume% of amorphous glass and 40 to 5% of filler, and the amorphous glass is composed of SiO ₂ component, B ₂ O ₃ component, and R ₂ O component. (However, R represents an alkali metal), the total weight of the SiO ₂ component, the B ₂ O ₃ component, and the R ₂ O component is 100%, and the SiO ₂ component is 88 wt% and the B ₂ O ₃ component is The composition of 12% by weight is the first composition, the composition of SiO ₂ is 82% by weight, the composition of the B ₂ O ₃ is 18% by weight is the third composition, the composition of SiO ₂ is 84% by weight, and the composition of B ₂ O _{3 is} B ₂ O _3. 10% by weight of ingredients,
The composition having 6% by weight of the R ₂ O component is the 10th composition, 90% by weight of the SiO ₂ component, 5% by weight of the B ₂ O ₃ component, and R ₂
The 11th composition is a composition in which the O component is 5% by weight, the SiO ₂ component is 89% by weight, the B ₂ O ₃ component is 10% by weight,
When the composition in which the R ₂ O component is 1 wt% is the fourth composition, in the SiO ₂ —B ₂ O ₃ —R ₂ O system triangular composition diagram, the points indicating the first composition and the third composition are Point, third composition and tenth composition, tenth composition and eleventh composition, eleventh composition and fourth composition , A point indicating the fourth composition and a point indicating the first composition, the wiring board having a composition indicated by a point inside (including on the line) surrounded by a line connecting the points. 41. The wiring board according to claim 40, wherein R is potassium. 42. A wiring board comprising a via and a wiring made of a conductor and a base material made of a ceramic, wherein the ceramic is 60 to 95 when the total volume of the ceramic is 100%.
A wiring board, which is a sintered body obtained by sintering amorphous glass having a volume% softening temperature of 850 to 1100 ° C. and 40 to 5% of a filler. 43. A wiring board comprising a via and a wiring made of a conductor and a base material made of a ceramic, wherein the ceramic has a total volume of the ceramic of 60 to 95.
It is a sintered body obtained by sintering volume% of amorphous glass and 40 to 5% of filler, and has a thermal expansion coefficient of 2.0 to 4.0 × 10 ⁻⁶ / ° C. Characteristic wiring board. 44. An electronic circuit device comprising: a wiring board provided with wiring made of a conductor; and an insulating layer made of ceramic; and an electronic circuit element mounted on the wiring board. The ceramic has a volume of 60 to 95. An electronic circuit device comprising: an amorphous glass having a softening temperature of 850 to 1100 ° C. and a filler of 40 to 5%. 45. An electronic module comprising: a wiring board provided with wiring made of a conductor and an insulating layer made of ceramic; and a semiconductor element mounted on the wiring board, wherein the ceramic has a volume of 60 to 95%. % Of softening temperature is 850-1100 degreeC, and the wiring board characterized by comprising 40-5% of filler, The module for electronic computers characterized by the above-mentioned. 46. A printed wiring board, and a computer module mounted on the printed wiring board, wherein the computer module includes a wiring board having wiring made of a conductor and an insulating layer made of ceramics. In an electronic computer including a semiconductor element mounted on the wiring board, the ceramic is composed of 60 to 95% by volume of an amorphous glass having a softening temperature of 850 to 1100 ° C. and 40 to 5% of a filler. An electronic computer comprising a wiring board characterized by the following.