JP2003078246A - Method of manufacturing glass ceramic substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of obtaining a glass-ceramic substrate, which gives high dimensional accuracy by surely constraining contraction in sintering ceramic green sheets, and which results in high reliability by being free from degradation of insulating property of glass-ceramic covering layers. SOLUTION: This method comprises steps of (i) forming a laminate 1 by laminating a plurality of glass-ceramic green sheets, on each surface of which a conductor pattern 2 is formed, and on each surface of the conductor pattern 2, forming a glass-ceramic covering layer 3 composed of glass-ceramic powder having a specified average grain size and grain-size distribution, an organic binder, and a solvent; (ii) laminating constraining green sheets containing hardly- sintered inorganic material and glass on both faces of the laminate; (iii) firing the laminate to form a glass-ceramic substrate having the constraining sheets; and (iv) removing the constraining sheets from the substrate. (v) Glass content of the constraining green sheets is the amount for binding the constraining sheets to the glass-ceramic green sheets and not allowing the constraining sheets to substantially contract within the laminating surfaces during the firing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a multi-layer glass ceramic substrate for mounting semiconductor LSIs, chip components, etc. and interconnecting them.

[0002]

2. Description of the Related Art In recent years, semiconductor LSIs, chip parts, etc. have been reduced in size and weight, and wiring boards for mounting them have been desired to be reduced in size and weight. In response to such demands, the multilayer ceramic substrate in which internal electrodes and the like are arranged in the substrate enables high-density wiring required and can be thinned, and thus is regarded as important in the electronics industry today. There is.

As a multilayer ceramic substrate, an insulating substrate made of an alumina sintered body and having a wiring layer made of a refractory metal such as tungsten or molybdenum formed on the surface or inside thereof has been widely used.

On the other hand, in the recent era of advanced information technology, the frequency band used is increasingly shifting to the high frequency band. In a high-frequency wiring board that transmits such a high-frequency signal, in order to transmit a high-frequency signal at high speed, it is required that the conductor forming the wiring layer has a low resistance, and the insulating board also has a lower dielectric constant. Required.

However, conventional refractory metals such as tungsten and molybdenum have large conductor resistance, slow signal propagation speed, and are difficult to propagate signals in a high frequency region of 30 GHz or more. Instead, it is necessary to use a low resistance metal such as copper, silver or gold. However, since the low-resistance metal as described above has a low melting point, it is necessary to bake at a low temperature of about 800 to 1000 ° C., so that the wiring layer made of the low-resistance metal is alumina that requires high temperature firing. It could not be fired at the same time. Further, since the alumina substrate has a high dielectric constant, it is not suitable for a high frequency circuit substrate.

Therefore, recently, attention has been paid to the use of glass ceramics obtained by firing a mixture of glass and ceramics (inorganic filler) as an insulating substrate. That is, since glass ceramics has a low dielectric constant, it is suitable as an insulating substrate for high frequencies, and since glass ceramics can be fired at a low temperature of 800 to 1000 ° C., a low resistance metal such as copper, silver, or gold is used as a wiring layer. There is an advantage that it can be used as.

The multi-layer glass ceramic substrate is made into a slurry by adding an organic binder, a plasticizer, a solvent, etc. to a mixture of glass and a filler, and after forming a glass ceramic green sheet with a doctor blade or the like, copper, silver, gold, etc. Forming a conductor pattern on the green sheet by printing a conductor paste containing a low-resistance metal powder, and then laminating a plurality of green sheets to form 800 to 100
It is obtained by firing at a temperature of 0 ° C.

However, the multilayer glass ceramic substrate is
There is a problem that shrinkage occurs due to sintering in the firing process. The degree of such shrinkage is not uniform, and the shrinkage rate and the shrinkage direction differ depending on the inorganic material for the substrate used, the green sheet composition, the variation in the particle size of the raw material powder, the conductor pattern, the internal electrode material, and the like. This causes some problems in the production of multilayer glass ceramic substrates.

First, when manufacturing a screen printing plate for printing internal electrodes, the size of the screen printing plate must be determined by back-calculating from the shrinkage ratio of the substrate. Since it is not constant, the screen plate must be remade for each manufacturing lot of the substrate, which is uneconomical and impractical. Further, in the multilayer glass ceramic substrate produced by the green sheet laminating method as described above, since the shrinkage rates in the longitudinal direction and the lateral direction in the laminating plane differ depending on the film forming direction of the green sheet, it is possible to produce the multilayer glass ceramic substrate. It will be even more difficult.

On the other hand, if an electrode having an unnecessarily large area is formed to allow the shrinkage error, high-density wiring cannot be performed.

In order to reduce these shrinkage changes,
Investigate the tendency of the shrinkage rate of the board due to the circuit design, manage the board material and the green sheet composition in the manufacturing process,
It is necessary to adequately control the stacking conditions such as variations in powder particle size, press pressure and temperature. However, it is generally said that an error in shrinkage of about ± 0.5% will inevitably occur.

This is a problem that is common to ceramics, glass ceramics, etc. regardless of the multilayer glass ceramic substrate. In order to solve such a problem, JP-A-4-243978 and JP-A-5-2886
In Japanese Patent Laid-Open No. 7-102666 and Japanese Patent Laid-Open No. 5-102666, the following (1)
A method of manufacturing a substrate including the steps (4) to (4) has been proposed. (1) A desired number of glass ceramic green sheets each containing a glass ceramic component and an organic component such as a binder and a plasticizer and having conductor patterns formed thereon are laminated, (2)
A constrained green sheet containing an inorganic material that does not sinter at the firing temperature of the glass ceramic component and an organic component such as a binder or a plasticizer is laminated on both surfaces or one surface of the obtained glass ceramic green sheet laminate, 3) Heating the laminated body of the glass ceramic green sheet and the constrained green sheet to remove organic components first, and then firing to form a glass ceramic substrate and a constrained sheet, respectively (4) Last First, the constraining sheet is removed from the glass ceramic substrate.

According to this method, since the constraining green sheet constrains the shrinkage of the glass ceramic green sheet during firing, the shrinkage occurs only in the thickness direction of the laminated body, and in the longitudinal and lateral directions of the laminated surface. It is considered that the shrinkage does not occur and the dimensional accuracy of the glass ceramic substrate is improved.

[0014]

In the above method, the glass-ceramic green sheet and the constraining green sheet are bonded to each other by an organic component such as a binder contained in the green sheet. But,
In the firing step (3), after the organic components such as the binder and the plasticizer are decomposed and volatilized, the powder in the constrained green sheet and the powder in the glass ceramic green sheet are simply brought into close contact with each other. There is only a weak bond between the sheets due to van der Waals forces.

Although such a weak bond has an advantage that the constraining sheet can be easily removed in the step (4), the constraining green sheet is removed from the glass ceramic green sheet laminate in the firing step (3). There is a risk of inadvertent peeling due to differences in thermal expansion.

If the constrained green sheet peels off during firing, it becomes impossible to prevent the sintering shrinkage of the glass ceramic green sheet. Further, even if the constrained green sheet is partly peeled off, the glass ceramic substrate is deformed because shrinkage occurs in the part.

Further, since the glass ceramic / green sheet laminate and the constraining green sheet have a small bonding force,
Depending on the adhesion state of them before firing and the permeability of the glass component in the glass-ceramic green sheet into the constrained green sheet depending on the type of the glass-ceramic component, the binding force thereof is likely to be uneven. If the binding force is uneven, the force for restraining the sintering shrinkage of the glass ceramic is also uneven, and uneven shrinkage occurs, and the glass ceramic substrate is warped or deformed. As a result, there is a problem that a substrate with high dimensional accuracy cannot be obtained.

Furthermore, a glass ceramic coating layer is often formed on the surface of the conductor pattern in order to form a pattern for mounting a semiconductor element or the like on the surface of the glass ceramic substrate. The glass-ceramic coating layer may cause minute cracks or the glass-ceramic coating layer may peel off when the constraining sheet covering the glass-ceramic coating layer is removed.

It is considered that this is because the glass-ceramic coating layer is not densified, and the pressure such as blast when removing the restraint sheet propagates from the surface to the voids existing inside the glass-ceramic coating layer. .

When the glass ceramic coating layer is cracked or peeled off, a resistor paste is screen-printed to form a resistor pattern on the substrate, or a component for mounting a semiconductor element or the like is mounted. When printing a solder paste, there is a problem that these printings become difficult. Further, there is a problem that cracks in the glass-ceramic coating layer progress due to heat stress caused by heat generation when a semiconductor element or the like is mounted and operated, and the insulation property is deteriorated and reliability is lowered.

An object of the present invention is to reliably restrain the sintering shrinkage within the laminated surface of the glass ceramic green sheet,
Another object of the present invention is to provide a method for obtaining a glass ceramic substrate having high dimensional accuracy and high reliability by suppressing the occurrence of cracks and peeling of the glass ceramic coating layer.

[0022]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to solve the above problems, (I) if a glass component is contained in the constrained green sheet, the glass component will burn. In the process, it acts as a binding material that joins the glass ceramic green sheet and the constraining green sheet, so that the binding force between them can be increased and the constraining green sheet can be prevented from peeling off. (II) Restraining green during firing Sintering shrinkage of the sheet itself can be substantially avoided by setting the glass content within a predetermined range, and as a result, the shrinkage of the glass ceramic / green sheet laminate is surely suppressed by (III) the restraining green sheet. That a glass ceramic substrate with high dimensional accuracy can be obtained, and (IV) glass ceramic of glass ceramic coating layer When the powder has an average particle size of 1 to 3 μm and the particle size distribution is 10% particle size D10, 50% particle size D50 and 90% particle size D90 in the number cumulative distribution (D90-D10) By setting / D50 ≦ 3, it is possible to suppress the occurrence of cracks and peeling of the glass ceramic coating layer, and it is possible to obtain a highly reliable glass ceramic substrate with high dimensional accuracy. The present invention has been completed and the present invention has been completed.

That is, in the method for producing a glass ceramic substrate of the present invention, (i) a plurality of glass ceramic green sheets containing an organic binder and having a conductor pattern formed on the surface thereof are laminated to laminate the glass ceramic green sheets. While making the body,
On the surface of the conductor pattern on the surface of the green sheet laminate, the average particle size is 1 to 3 μm, and the particle size distribution is 10% particle size D10 and 50% particle size D5 in the number cumulative distribution.
0, 90% (D90-D10) / D5 when the particle size is D90
Consisting of a glass ceramic paste in which 0 ≦ 3, a glass ceramic powder, an organic binder and a solvent are mixed,
A step of forming a glass ceramic coating layer exposing a part of the conductor pattern, and (ii) a constraining green containing a hardly-sinterable inorganic material, glass and an organic binder on both surfaces of the glass ceramic green sheet laminate. A step of laminating sheets, and (iii) a step of removing the organic component from the laminated body of the constrained green sheet and the glass-ceramic / green-sheet laminated body, and then firing to produce a glass-ceramic substrate holding the constrained sheet. And (iv) removing the constraining sheet from the glass-ceramic substrate, and (v) the glass content of the constraining green sheet is such that the constraining green sheet is combined with the glass-ceramic green sheet during the firing. It is characterized in that the amount of the constrained green sheet does not substantially shrink within the lamination plane.

Here, "not substantially shrink" means
Shrinkage of constrained green sheets is less than 1%, preferably 0.8
% Or less, more preferably 0.5% or less. The "in-plane" means a plane defined by the X direction and the Y direction when the thickness direction is the Z direction in the three-dimensional coordinate, and specifically, the longitudinal direction and the lateral direction of the sheet. Means

In the present invention, the softening point of the glass contained in the constrained green sheet is preferably not higher than the firing temperature of the glass ceramic green sheet laminate. As a result, the glass in the constrained green sheet is softened in the firing step, and the bonding strength is increased.

The softening point of the glass contained in the constrained green sheet is preferably higher than the removal temperature of the organic component. When the softening point of the glass is lower than the removal temperature of the organic component, the removal path for passing the decomposed / volatilized organic component may be blocked by the softened glass.

The glass content in the constrained green sheet is preferably 0.5 to 15% by weight based on the total inorganic components in the constrained green sheet. Usually, this range is an amount that binds to the glass-ceramic green sheet during firing and does not substantially shrink the constraining green sheet within its laminating plane, but it is not necessarily limited to this range and is used. The glass content changes depending on the type of glass.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The glass-ceramic green sheet of the present invention is a mixture of glass powder, filler powder (ceramic powder), organic binder, plasticizer, organic solvent and the like.

As the glass component, for example, SiO₂-B₂
O₃System, SiO₂-B₂O₃-Al₂O₃System, SiO₂-B₂O
₃-Al₂O₃-MO system (however, M is Ca, Sr, Mg,
Ba or Zn), SiO₂-Al₂O₃-M¹O-
M²O type (however, M¹And M ²Are the same or different and are C
a, Sr, Mg, Ba or Zn), SiO₂−
B₂O₃-Al₂O₃-M¹OM²O type (however, M¹and
M²Is the same as above), SiO₂-B₂O₃-M³ ₂O system
(However, M³Represents Li, Na or K), SiO₂−
B₂O₃-Al₂O₃-M³ ₂O type (however, M³Is the same as above
Pb-based glass, Bi-based glass, and the like.
It

As the filler, for example, Al
_At least one selected from ₂ O ₃ , SiO ₂ , composite oxide of ZrO ₂ and alkaline earth metal oxide, composite oxide of TiO ₂ and alkaline earth metal oxide, Al ₂ O ₃ and SiO _2. Examples thereof include complex oxides containing (for example, spinel, mullite, cordierite).

The mixing ratio of the glass and the filler is preferably 40:60 to 99: 1 by weight.

As the organic binder to be mixed in the glass ceramic green sheet, those conventionally used in ceramic green sheets can be used.
For example, acrylics (homopolymers or copolymers of acrylic acid, methacrylic acid or their esters, specifically acrylic acid ester copolymers, methacrylic acid ester copolymers, acrylic acid ester-methacrylic acid ester copolymers Etc.), polyvinyl butyral type, polyvinyl alcohol type, acryl-styrene type, polypropylene carbonate type, cellulose type homopolymers or copolymers.

The glass-ceramic green sheet is prepared by adding a predetermined amount of a plasticizer and a solvent (organic solvent, water, etc.) to the above-mentioned glass powder, filler powder and organic binder to obtain a slurry, which is then doctor blade. , Rolling, calender roll, die brace, etc., thickness about 50-500μ
It is obtained by molding into m.

To form a conductor pattern on the surface of the glass ceramic green sheet, for example, a paste of conductor material powder is printed by a screen printing method or a gravure printing method, or a metal foil having a predetermined pattern is transferred. And the like. As the conductor material, for example, one kind or two kinds or more of Au, Ag, Cu, Pd, Pt and the like can be mentioned. In the case of two kinds or more, a mixture, an alloy,
It may be in any form such as coating.

The conductor pattern on the surface also includes a portion where a through conductor such as a via conductor or a through hole conductor for connecting conductor patterns between upper and lower layers is exposed on the surface. These through conductors are formed by means of embedding a paste (conductor paste) of conductive material powder in a through hole formed in a glass ceramic green sheet by punching or the like by printing.

For lamination of glass ceramic green sheets, a method of applying heat and pressure to the stacked green sheets to perform thermocompression bonding, or applying an adhesive composed of an organic binder, a plasticizer, a solvent, etc. between the sheets, and performing thermocompression bonding. It is possible to adopt a method of doing so.

Next, in order to form a pattern for mounting a semiconductor element or the like on the surface of the obtained glass-ceramic / green sheet laminate, a part of it is exposed on the surface of the conductor pattern on the surface of the laminate. A glass-ceramic coating layer having a substantially square opening of about 2 to 5 mm □ is formed.

It should be noted that the glass ceramic coating layer should have a substantially square shape with its corners having a non-rectangular shape as the shape of the opening, and the restraint sheet laminated to cover the glass ceramic coating layer is removed. At this time, it is preferable in that the occurrence of partial cracks in the glass ceramic coating layer starting from the opening is suppressed.

Further, it is preferable that the corners of the substantially quadrangular opening have an arc shape with a radius of 0.02 to 1 mm in order to suppress the occurrence of partial cracks in the glass ceramic coating layer when the constraining sheet is removed. If the radius of the arc-shaped corner portion is less than 0.02 mm, the pressure when removing the restraint sheet tends to concentrate on the corner portion, and partial cracks or peeling generated from the corner portion tends to occur. On the other hand, the radius of the arc-shaped corner is 1 m
When it exceeds m, the shape of the opening, which is usually formed in a size of about 2 to 5 mm □, becomes close to a circular shape, and it tends to be difficult to mount and mount a quadrangular semiconductor element.

To form a glass-ceramic coating layer on the surface of a glass-ceramic green sheet on which a conductor pattern is formed, for example, a raw material powder such as glass powder or alumina powder is mixed with an appropriate organic binder, plasticizer and solvent. Made into a paste (coating paste)
Examples of the method include printing by screen printing or gravure printing.

The glass-ceramic powder used for the glass-ceramic coating layer has an average particle size of 1 to 3 μm and a particle size distribution (D90-D10) / D50 of 3 or less. It is preferable in that it suppresses the occurrence of partial cracks when removing the constraining sheet that has been laminated.

If the average particle size of the glass ceramic powder used for the glass ceramic coating layer is less than 1 μm, the dispersion of the glass ceramic powder during the production of the glass ceramic paste will be poor, and a large amount of solvent or binder will be required. The glass ceramic coating layer after firing tends to be difficult to densify, the void ratio may exceed 5%, and cracks and peeling tend to occur easily from the voids present inside the glass ceramic coating layer. On the other hand, if the average particle size exceeds 3 μm, the sintered particles of the glass ceramic powder are hard to grow, the glass ceramic coating layer tends to be difficult to densify, and the void ratio is 5 or less.
%, And cracks and peeling tend to occur easily from the voids present inside the glass-ceramic coating layer.

Further, even if the average particle diameter of the glass ceramic used for the glass ceramic coating layer is 1 to 3 μm, if the particle size distribution (D90-D10) / D50 exceeds 3, the glass ceramic used for preparing the glass ceramic paste Since the dispersion of the powder becomes poor, a large amount of solvent and binder are required, the glass ceramic coating layer after firing tends to be difficult to densify, and the void ratio may exceed 5%. There is a tendency for cracks and peeling to easily occur from the voids present in.

The void ratio showing the denseness of the glass-ceramic coating layer can be obtained by observing the cross section with an electron microscope (SEM) or the like.

The constrained green sheet in the present invention is obtained by molding a slurry obtained by adding an organic binder, a plasticizer, a solvent and the like to an inorganic component composed of a hardly-sinterable inorganic material and glass. Al ₂ O ₃ and S are used as the non-sinterable inorganic material.
At least one selected from iO ₂ may be mentioned, but the invention is not limited thereto.

The glass added to the constrained green sheet is not particularly limited, and the same glass as the glass compounded in the glass ceramic green sheet described above can be used. Further, the glass in the constrained green sheet may have the same composition as the glass in the glass ceramic green sheet or may have a different composition.

The softening point of the glass in the constrained green sheet is preferably lower than the firing temperature of the glass-ceramic / green sheet laminate and higher than the decomposition / volatilization temperature of the organic component in the constrained green sheet. Specifically, the softening point of the glass in the constrained green sheet is preferably about 450 to 1100 ° C. If the softening point of the glass is less than 450 ° C, the removal of the organic components from the glass-ceramic green sheet will block the removal route of the organic components decomposed and volatilized, and the organic components will be completely removed. It may not be possible. On the other hand, the softening point of glass is 1100 ℃
If it exceeds, there is a possibility that it will not act as a binder to the ordinary glass-ceramic green sheet under the firing conditions.

The constrained green sheet can be obtained by molding using an organic binder, a plasticizer, a solvent, etc. in the same manner as in the production of the glass ceramic green sheet. As the organic binder, the plasticizer and the solvent, the same materials as those used for the glass ceramic green sheet can be used. Here, the plasticizer is added in order to impart flexibility to the constrained green sheet and enhance the adhesiveness with the glass ceramic green sheet during lamination.

The thickness of the constraining green sheet laminated on both sides of the glass ceramic green sheet is preferably 10% or more with respect to the thickness of the glass ceramic green sheet laminate only on one side, and more than 10%. If it is thin, the restraint of the restraint green sheet may be reduced. Further, in consideration of facilitating the volatilization of organic components and removing the constraining sheet from the glass ceramic substrate, the thickness of the constraining green sheet should be about 200% or less of the thickness of the glass ceramic / green sheet laminate. . Further, the constraining sheet to be laminated may be a single sheet, or a plurality of sheets may be laminated so as to have a predetermined thickness.

In order to laminate the formed constrained green sheets on both sides of the glass-ceramic green sheet, heat and pressure are applied to the stacked green sheets to perform thermocompression bonding, and bonding using an organic binder, a plasticizer, a solvent, etc. A method of applying the agent between the sheets and thermocompression-bonding can be adopted. When an adhesive layer is interposed between the sheets, the adhesive layer may contain the same glass component as that of the constrained green sheet to enhance the bonding force between the sheets.

After stacking the constrained green sheets, the organic components are removed and baked. The organic components are removed by heating the laminate in the temperature range of 100 to 800 ° C to decompose and volatilize the organic components. Although the firing temperature varies depending on the glass ceramic composition, it is usually in the range of about 800 to 1100 ° C. Firing is usually performed in the air, but when Cu is used as the conductor material, the organic components are removed in a nitrogen atmosphere containing steam at 100 to 700 ° C., and then firing is performed in a nitrogen atmosphere.

During firing, a load may be applied by placing a weight on the upper surface of the laminate to prevent warpage. A load of about 50 Pa to 1 MPa is suitable. If the load is less than 50 Pa, the warpage suppressing effect of the laminate may not be sufficient. Further, if the load exceeds 1 MPa, the weight to be used becomes large, so that it may not enter the firing furnace, or even if it enters the firing furnace, the heat capacity may be insufficient and firing may not be possible. As the weight, it is preferable to use, for example, porous ceramics or metal so as not to prevent volatilization of decomposed organic components. A porous weight may be placed on top of the stack and a non-porous weight placed on top of it.

After firing, the restraint sheet is removed. The removing method is not particularly limited as long as it can remove the restraint sheet bonded to the surface of the glass ceramic substrate, and includes, for example, ultrasonic cleaning, polishing, water jet, sand blasting, wet blasting (abrasive particles and water by air pressure). And the like).

Since the shrinkage during firing of the obtained multilayer glass ceramic substrate is suppressed only in the thickness direction by the constraining green sheet, the shrinkage in the laminated plane is about 0.
It can be suppressed to 5% or less, and since the glass ceramic green sheet is uniformly and surely restrained over the entire surface by the restraint green sheet, warping or deformation occurs due to partial peeling of the restraint green sheet. The glass-ceramic powder of the glass-ceramic coating layer has an average particle size of 1
.About.3 .mu.m and the particle size distribution (D90-D10) / D50 is 3 or less, the glass-ceramic coating layer can be a dense sintered body having a void ratio of 5% or less. The pressure at the time of removing the sheet can be favorably absorbed, and the occurrence of partial cracks or peeling of the glass ceramic coating layer can be suppressed.

[0055]

EXAMPLES The method of the present invention will be described in detail below with reference to Examples, Comparative Examples and Test Examples, but the present invention is not limited to the following Examples.

FIG. 2 is a sectional view showing an example of a glass ceramic / green sheet laminate obtained by the manufacturing method of the present invention. 1 is a glass ceramic / green sheet laminate and 2 is a glass ceramic / green sheet laminate. 1
The conductor pattern on the surface of the conductor pattern, 3 is a glass ceramic coating layer formed on the surface of the conductor pattern 2, and 3a is an opening thereof. <Example 1> As a glass ceramic component, SiO ₂ -
60 wt% of Al ₂ O ₃ —MgO—B ₂ O ₃ —ZnO based glass powder, 20 wt% of CaZrO ₃ powder, 17 wt% of SrTiO ₃ powder and ₃ wt% of Al ₂ O ₃ powder were used. To 100 parts by weight of this glass-ceramic component, 12 parts by weight of an acrylic resin as an organic binder, 6 parts by weight of a phthalic acid-based plasticizer and 30 parts by weight of toluene as a solvent were added and mixed by a ball mill method to obtain a slurry. Using this slurry, a glass ceramic green sheet having a thickness of 300 μm was formed by the doctor blade method.

Then, a conductor pattern 2 was formed on this green sheet by screen printing using silver-palladium paste. As the conductor paste, 100: alloy powder having an Ag: Pd weight ratio of 85:15 (average particle size 1.0 μm)
₂ parts by weight of Al ₂ O ₃ powder and 2 parts by weight of glass powder having the same composition as the above glass, and a predetermined amount of ethyl cellulose resin and terpineol as vehicle components are added to obtain an appropriate viscosity by three rolls. The above mixture was used.

Next, a part of the conductor pattern 2 is exposed on the surface of the conductor pattern 2 on the surface of the glass-ceramic / green sheet laminate by applying the glass-ceramic coating layer 3.
An arc-shaped 3 mm square opening 3 a having a corner radius of 0.5 mm was provided, and a glass ceramic paste was used for screen printing.

The glass-ceramic paste has an average particle size of 1.5 μm and its particle size distribution (D90-D10) / D50.
No. 2 glass ceramic powder, 12 parts by weight of an acrylic resin, 2 parts by weight of a phthalic acid-based plasticizer and terpineol as a solvent were mixed and mixed with a three-roll so as to have an appropriate viscosity.

On the other hand, 95% by weight of Al ₂ O ₃ powder as an inorganic component and SiO ₂ —Al ₂ O ₃ —MgO—B ₂ O ₃ having a softening point of 720 ° C.
A ZnO-based glass powder (5% by weight) was used to prepare a slurry in the same manner as the glass ceramic green sheet, and then the slurry was molded to obtain a constrained green sheet having a thickness of 250 μm.

A glass ceramic green sheet laminate 1 is obtained by stacking a predetermined number of glass ceramic green sheets for the surface layer and the glass ceramic green sheet for the inner layer on the surface of which the conductor pattern 2 and the glass ceramic coating layer 3 are formed. Further, the constrained green sheets were superposed on both sides thereof, and pressure-bonded at a temperature of 55 ° C. and a pressure of 20 MPa to obtain a laminate.

The obtained laminated body was placed on an alumina setter, and a porous ceramic plate having a porosity of 75% was placed as a weight on the laminated body, whereby the laminated body was evenly averaged.
After applying a load of 100 Pa and heating in air at 500 ° C. for 2 hours to remove organic components, firing was performed at 900 ° C. for 1 hour. After firing, the constraining sheets were attached to both sides of the glass ceramic substrate. In this state, the binding sheet was not peeled off even if tapped lightly.

The restraint sheet adhering to the surface of the glass ceramic substrate was removed by a wet blast method in which a mixture of spherical Al ₂ O ₃ fine powder and water was projected by high-pressure air pressure. The surface of the glass ceramic substrate after removing the restraint sheet becomes a smooth surface having a surface roughness Ra of 1 μm or less,
There was no problem with the solder wettability of the conductor. Moreover, neither peeling nor cracking occurred in the glass ceramic coating layer 3.

Further, the shrinkage of the obtained glass ceramic substrate in the laminating plane was 0.5% or less, and the substrate was not warped or deformed. <Comparative Examples 1 to 4> Comparative Examples 1 to 4 except that the glass ceramic coating layer 3 was formed using a glass ceramic paste containing glass ceramic powder having the average particle size and particle size distribution shown in Table 1. Glass ceramic substrates 1 to 4 were obtained.

As a result, in the glass ceramic substrates of Comparative Examples 1 to 4, since the glass ceramic coating layer 3 was not densified, the glass ceramic coating layer 3 was peeled off when the restraint sheet attached to the surface was removed. .

Further, the denseness of the glass ceramic coating layer 3 of the obtained glass ceramic substrate was compared by the void ratio by observing the cross section with an electron microscope.

[0067]

[Table 1]

It can be seen from Table 1 that the glass ceramic coating layers 3 of Comparative Examples 1 to 4 have a large void ratio and are not densified. <Examples 2 and 3> A glass ceramic substrate was obtained in the same manner as in Example 1 except that constrained green sheets were produced using glasses having softening points of 600 ° C and 700 ° C, respectively.

When the constraining sheet was removed, neither peeling nor cracking occurred in the glass ceramic coating layer 3. <Comparative Example 5> A glass ceramic substrate was obtained in the same manner as in Example 1 except that a constrained green sheet containing no glass was produced. <Comparative Example 6> A glass ceramic substrate was obtained in the same manner as in Example 1 except that a constrained green sheet was produced using glass having a softening point of 920 ° C. <Comparative Example 7> A glass ceramic substrate was obtained in the same manner as in Example 1 except that a constrained green sheet was produced using glass having a softening point of 400 ° C.

As a result, the glass-ceramic substrates obtained in Examples 2 and 3 had a shrinkage in the laminated plane of 0.5% or less (that is, a shrinkage rate of 99.5% or more) as in Example 1.
No warp or deformation was observed on the substrate. Moreover, neither peeling nor cracking occurred in the glass ceramic coating layer 3.

On the other hand, in the glass ceramic substrates obtained in Comparative Examples 5 and 6, the constrained green sheets used did not contain glass or contained glass having a softening point higher than the firing temperature. In each case, the restraint green sheet was easily peeled off from the glass ceramic substrate after firing. In addition, since the bonding strength between the glass ceramic green sheet and the constraining green sheet is weak, the shrinkage rate in the laminated surface of the glass ceramic substrate is 85%.
To some extent, the glass-ceramic substrate was significantly deformed because only part of the substrate was bonded to the constraining sheet.

On the other hand, in Comparative Example 7, since the glass contained in the constrained green sheet has a low softening point, the organic component is not completely removed, and therefore the shrinkage in the laminated surface of the glass ceramic substrate is 0.5% or less. Although it was good, the color tone of the glass ceramic substrate became gray. <Examples 4 to 7> SiO was used as a glass ceramic component.
_{2 -MgO-CaO-Al 2 O} 3 based glass powder 70 wt%,
30% by weight of Al ₂ O ₃ powder was used. Acrylic resin as an organic binder is added to 100 parts by weight of this glass-ceramic component.
9.0 parts by weight, 4.5 parts by weight of a phthalic acid-based plasticizer and 30 parts by weight of toluene as a solvent were added and mixed by a ball mill method to obtain a slurry. Using this slurry, a glass ceramic green sheet having a thickness of 300 μm was formed by the doctor blade method.

Then, Example 1 was placed on this green sheet.
The same silver-palladium paste was used to form a conductor pattern by screen printing.

Next, the same glass-ceramic paste as in Example 1 was used to form a similar glass-ceramic coating layer 3 by screen printing.

On the other hand, Al ₂ O ₃ powder and SiO ₂ —MgO—CaO—Al ₂ O ₃ glass powder having a softening point of 720 ° C. were used as the inorganic components in the proportions shown in Table 2, respectively, and the above glass ceramic green was used. A slurry was prepared in the same manner as the sheet, and was then molded to obtain a constrained green sheet having a thickness of 250 μm.

A glass ceramic / green sheet laminate 1 was obtained by stacking a predetermined number of glass ceramic / green sheets for the surface layer having the conductor pattern 2 and the glass ceramic coating layer 3 on the surface and glass ceramic / green sheets for the inner layer. Further, the constrained green sheets were superposed on both sides thereof, and pressure-bonded at a temperature of 55 ° C. and a pressure of 20 MPa to obtain a laminate. This stack has a size of 150 mm x 120
It was a rectangle of mm.

The obtained laminated body was placed on an alumina setter, and a porous ceramic plate having a porosity of 50% was placed on the laminated body so that an average load of 50 Pa was applied to the laminated body. After heating in air at 500 ° C. for 2 hours to remove the organic component, it was baked at 850 ° C. for 1 hour. Then, the restraint sheet attached to the surface of the glass ceramic substrate was removed. The surface of the obtained glass ceramic substrate is
The surface roughness Ra was a smooth surface of 1 μm or less, and there was no problem with the solder wettability of the conductor. Moreover, when the constraining sheet was removed, neither peeling nor cracking occurred in the glass ceramic coating layer 3.

Table 2 also shows the shrinkage ratio of the obtained glass-ceramic substrate in the laminating plane. No warp or deformation was observed in the glass ceramic substrate.

[0079]

[Table 2]

From Table 2, each restraint green of Examples 4 to 7
The glass-ceramic substrate obtained using the sheet is baked.
Suppresses shrinkage and warpage during growth, and has high dimensional accuracy
You can see that In addition, in the results shown in Table 2, the warp is
High warpage using laser optical non-contact 3D shape measuring device
Is measured. <Example 8> Instead of AgPd alloy powder in the conductor paste
Cu powder is used for the nitrogen atmosphere containing steam at 100-700 ℃.
Remove organic components in ambient air, then in nitrogen atmosphere
A glass cell was prepared in the same manner as in Example 4 except that the baking was performed in
A lamic substrate was obtained. As in the case of Example 4, the yield within the lamination plane
Shrinkage is 0.5% or less (that is, shrinkage rate is 99.5% or more)
No warp or deformation was observed on the substrate. Also restraint
When removing the sheet, the glass ceramic coating layer 3
No peeling or cracking occurred. <Test Example 1> (Shrinkage test of restraint green sheet) Al as inorganic component
₂O₃Powder and softening point of 720 ℃ SiO₂-MgO-CaO-A
l ₂O₃Using the glass powder and each at a predetermined ratio,
Furthermore, 9.0 parts by weight of acrylic resin as an organic binder,
4.5 parts by weight of phthalic acid plasticizer and toluene 3 as solvent
Add 0 parts by weight and mix them in a ball mill to make a slurry.
- Thick this slurry by doctor blade method
A 250 μm thick restraint green sheet was formed.

This constrained green sheet was placed alone on an alumina setter, heated in air at 500 ° C. for 2 hours to remove organic components, and then fired at 850 ° C. for 1 hour.

FIG. 1 shows the relationship between the shrinkage ratio in the plane of the obtained constraining sheet and the glass addition amount. In addition, the shrinkage ratio shows the average value (n = 5) of the shrinkage ratios in the width direction and the flow direction excluding the thickness direction of the restraint sheet and the variation thereof.
(Dimension after firing) × 100 / (Dimension before firing). Further, the flow direction means the film forming direction of the green sheet, and the width direction means the direction orthogonal to the film forming direction.

As shown in FIG. 1, in order to set the shrinkage ratio to 99.5% or more, that is, to suppress the shrinkage of the restraint sheet to 0.5% or less, the amount of glass added to the restraint green sheet is set to about 15% by weight or less. It turns out that is desirable. If the amount of glass added exceeds 15% by weight, the shrinkage variation tends to increase. However, when the amount of added glass is small, the constraining property of the glass ceramic green sheet by the constraining green sheet deteriorates (Comparative Example 5 above).
It is necessary to determine the glass addition amount that does not reduce the restraint property, and in the present invention, 0.5 to 15% by weight is set as a preferable range. <Test Example 2> SiO ₂ -Al ₂ O ₃ -MgO as glass
-B ₂ O ₃ except for using the -ZnO based glass powder Test Example 1
Similarly, when the relationship between the glass addition amount and the shrinkage ratio was examined, the shrinkage ratio of the constrained green sheet was 99.5% or more when the glass addition amount was 15% by weight or less, and the glass addition amount was 10% or less.
Below 9% by weight, about 99.8% was maintained.

[0084]

EFFECTS OF THE INVENTION According to the present invention, the constraining green sheets that are combined with the laminated body and do not shrink substantially during firing are laminated and fired on both sides of the glass-ceramic / green sheet laminated body. It is possible to surely suppress the shrinkage in the lamination plane of the green sheet substrate, and to cover the conductor pattern on the surface of the glass ceramic green sheet laminate, and to expose a part of the substantially rectangular shape. The glass-ceramic powder used for the glass-ceramic coating layer having an opening of 1 has an average particle diameter of 1 to 3 μm, and its particle size distribution (D90-
Since D10) / D50 is set to 3 or less, the occurrence of cracks and peeling of the glass ceramic coating layer can be suppressed, the dimensional accuracy is high without warpage or deformation, and the insulating property of the glass ceramic coating layer is high. There is an effect that a highly reliable glass-ceramic substrate free of deterioration can be obtained.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the amount of glass added to a constrained green sheet and the shrinkage rate.

FIG. 2 is a cross-sectional view showing an example of a glass ceramic / green sheet laminate obtained by the method for producing a glass ceramic substrate of the present invention.

[Explanation of symbols]

1-Glass ceramic green sheet laminate 2 ... Conductor pattern 3 ... Glass-ceramic coating layer

Claims (5)

[Claims] 1. A glass ceramic green sheet laminate is produced by laminating a plurality of glass ceramic green sheets containing an organic binder and having a conductor pattern formed on the surface thereof, and the glass ceramic green sheet laminate. On the surface of the conductor pattern, the average particle size is 1 to 3 μm, and the particle size distribution is 10% particle size D10 and 50% particle size D5 in the number cumulative distribution.
When the particle size of 0, 90% is D90 (D90-D1
0) / D50 ≦ 3, a step of forming a glass-ceramic coating layer which is made of a glass-ceramic paste in which an organic binder and a solvent are mixed, and exposes a part of the conductor pattern, and the glass-ceramic green. A step of laminating a constrained green sheet containing a hardly-sinterable inorganic material, glass and an organic binder on both sides of the sheet laminate, and an organic component from the laminated body of the constrained green sheet and the glass ceramic green sheet laminate. Removing, and then firing to produce a glass-ceramic substrate holding the constraining sheet, and removing the constraining sheet from the glass ceramic substrate, the glass content of the constraining green sheet is constrained during the firing Combine the green sheet with the glass ceramic green sheet A method for producing a glass-ceramic substrate, characterized in that the amount of the constrained green sheet does not substantially shrink within the laminating plane. 2. The method for producing a glass ceramic substrate according to claim 1, wherein the softening point of the glass contained in the constrained green sheet is not higher than the firing temperature of the glass ceramic green sheet laminate. . 3. The method for manufacturing a glass ceramic substrate according to claim 1, wherein the softening point of the glass contained in the constrained green sheet is higher than the volatilization temperature of the organic component. 4. The glass content in the constrained green sheet is 0.5 to 1 of all inorganic components in the constrained green sheet.
The method for producing a glass ceramic substrate according to claim 1, wherein the amount is 5% by weight. 5. The method for manufacturing a glass ceramic substrate according to claim 1, wherein the thickness of the constrained green sheet is 10% or more with respect to the thickness of the glass ceramic green sheet laminate on one surface.